Treatment liquid

ABSTRACT

The present invention provides a treatment liquid for a semiconductor device, which has excellent temporal stability of residue removal performance as well as excellent anticorrosion performance for an object to be treated. The treatment liquid of an aspect of the present invention is a treatment liquid for a semiconductor device contains one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and a hydroxylamine salt, an organic basic compound, an alcohol-based solvent, and a surfactant, in which a content of the alcohol-based solvent with respect to a total mass of the treatment liquid is 40% to 85% by mass, and a pH is 8 or higher.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2019/006981 filed on Feb. 25, 2019, which claims priority under 35U.S.C. § 119(a) to Japanese Patent Application No. 2018-069565 filed onMar. 30, 2018. The above application is hereby expressly incorporated byreference, in its entirety, into the present application.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a treatment liquid. In particular, thepresent invention relates to a treatment liquid which can be suitablyused for the manufacture of a semiconductor device.

2. Description of the Related Art

Semiconductor devices such as charge-coupled devices (CCDs) and memoriesare manufactured by forming fine electronic circuit patterns onsubstrates using photolithography technology. Specifically, thesemiconductor devices are manufactured by forming a resist film on alaminate that has a metal film serving as a wiring material, an etchingstop layer, and an interlayer insulating layer on a substrate, andcarrying out a photolithographic step and a dry etching step (forexample, a plasma etching treatment).

Furthermore, nowadays, a metal material-based resist film (a so-calledmetal hard mask) such as TiN and AlOx has been studied as the resistfilm in order to realize further miniaturization of semiconductordevices. In a case where the metal hard mask is used as the resist film,a dry etching step (for example, a plasma etching treatment) isperformed using the metal hard mask as a mask and a step of formingholes based on a pattern shape of the metal hard mask and exposing asurface of a metal film serving as a wiring film are usually performed.

Dry etching residues (in a case where a metal hard mask is used as aresist film, a large amount of metal components such as a titanium-basedmetal are included as the residual components, and on the other hand, ina case where a photoresist film is used, a large amount of organiccomponents are included as the residual components) adhere to asubstrate which has been subjected to a dry etching step. These residuesare generally removed using a treatment liquid so as not to interferewith the next step.

For example, US2016/0122695A discloses a cleaning liquid forlithography, which contains hydroxylamine, at least one organic basiccompound selected from the group consisting of a compound and aquaternary ammonium hydroxide, and water, and has a pH of 8 or more.

SUMMARY OF THE INVENTION

The present inventors have examined the cleaning liquid (treatmentliquid) described in US2016/0122695A, and have thus found thatperformance thereof is likely to be significantly reduced after storageover time. That is, they have also found that it is necessary to improvethe temporal stability of the residue removal performance of thetreatment liquid.

Moreover, on the other hand, the treatment liquid has been required tohave suppressed corrosion (anticorrosion performance) of wiring metals(which may be any of a metal, a metal nitride, an alloy, and the like;and may be, for example, W or Co used as a wiring metal, or a formcontaining such a metal) which may contain an object to be treated.

Therefore, an object of the present invention is to provide a treatmentliquid for a semiconductor device, which has excellent temporalstability of residue removal performance as well as excellentanticorrosion performance for an object to be treated.

The present inventors have conducted intensive studies to solve theproblems, and as a result, have found that the objects can beaccomplished by the following configuration.

[1] A treatment liquid for a semiconductor device, comprising:

one or more hydroxylamine compounds selected from the group consistingof hydroxylamine and a hydroxylamine salt;

an organic basic compound;

an alcohol-based solvent; and

a surfactant,

in which a content of the alcohol-based solvent is 40% to 85% by masswith respect to a total mass of the treatment liquid, and

a pH is 8 or higher.

[2] The treatment liquid as described in [1],

in which a content of the hydroxylamine compound is 1% to 20% by masswith respect to the total mass of the treatment liquid.

[3] The treatment liquid as described in [1] or [2],

in which a mass ratio of a content of the hydroxylamine compound to acontent of the surfactant is 1 to 1,000.

[4] The treatment liquid as described in any one of [1] to [3],

in which the organic basic compound includes one or more selected fromthe group consisting of tetramethylammonium hydroxide,tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide,tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine,1,8-diazabicyclo[5.4.0]-7-undecene, and 1,4-diazabicyclo[2.2.2]octane.

[5] The treatment liquid as described in any one of [1] to [4],

in which the organic basic compound contains a tertiary amine compound,

the tertiary amine compound contains a tertiary amino group other than atertiary amino group contained in a nitrogen-containing non-aromaticring, and

a content of the tertiary amine compound is 1 ppt by mass to 5 ppm bymass with respect to the total mass of the treatment liquid.

[6] The treatment liquid as described in any one of [1] to [5],

in which a mass ratio of a content of the organic basic compound to acontent of the surfactant is 1 to 150.

[7] The treatment liquid as described in any one of [1] to [6],

in which the surfactant is a cationic surfactant.

[8] The treatment liquid as described in [7],

in which the cationic surfactant contains a quaternary nitrogen atom.

[9] The treatment liquid as described in any one of [1] to [7],

in which the surfactant contains one or more selected from the groupconsisting of cetyltrimethylammonium bromide, cetylpyridinium chloride,benzethonium chloride, chlorhexidine dihydrochloride,distearyldimethylammonium chloride, benzalkonium chloride, dequaliniumchloride, dodecyltrimethylammonium chloride, octadecylaminehydrochloride, and dodecylpyridinium chloride.

[10] The treatment liquid as described in any one of [1] to [9],

in which a content of the surfactant is 1 ppm by mass to 0.5% by masswith respect to the total mass of the treatment liquid.

[11] The treatment liquid as described in any one of [1] to [10],

in which the alcohol-based solvent contains an alkoxy group.

[12] The treatment liquid as described in any one of [1] to [10],

in which the alcohol-based solvent contains one or more selected fromthe group consisting of 3-methoxy-3-methyl 1-butanol, furfuryl alcohol,glycerin, 2-methyl-2,4-pentanediol, ethylene glycol, 1,2-propanediol,ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,and dipropylene glycol monomethyl ether.

[13] The treatment liquid as described in any one of [1] to [12],further comprising an alkyl halide compound,

in which a content of the alkyl halide compound is 1 ppt by mass to 5ppm by mass with respect to the total mass of the treatment liquid.

[14] The treatment liquid as described in any one of [1] to [13],further comprising a reducing agent.

[15] The treatment liquid as described in [14],

in which the reducing agent is one or more reducing agents selected fromthe group consisting of catechol and a derivative thereof, and amercaptan compound.

[16] The treatment liquid as described in any one of [1] to [15],further comprising acetic acid,

in which a content of the acetic acid is 1 ppt by mass to 0.1% by masswith respect to the total mass of the treatment liquid.

[17] The treatment liquid as described in any one of [1] to [16],further comprising another organic acid other than acetic acid.

[18] The treatment liquid as described in any one of [1] to [17],further comprising metal-containing particles,

in which the metal-containing particle contains one or more metalcomponents selected from the group consisting of Na, Ca, Fe, and Cr,

a particle diameter of the metal-containing particle is 0.02 to 0.05 μm,and

a content of the metal-containing particles is 10 ppt by mass to 10 ppbby mass with respect to the total mass of the treatment liquid.

[19] The treatment liquid as described in any one of [1] to [18], usedas a cleaning liquid for removing etching residues, a solution forremoving a resist film used for pattern formation, or a cleaning liquidfor removing residues from a substrate after chemical mechanicalpolishing.

[20] The treatment liquid as described in any one of [1] to [19], usedfor a treatment of a substrate having a metal layer containing one ormore selected from the group consisting of W and Co.

According to the present invention, it is possible to provide atreatment liquid for a semiconductor device, which has excellenttemporal stability of residue removal performance as well as excellentanticorrosion performance for an object to be treated.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view showing an example of alaminate which can be applied to a substrate cleaning method using atreatment liquid of an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention will be described in detail.

The description of the constituents described below is sometimes madebased on representative embodiments of the present invention, but thepresent invention is not limited to such embodiments.

In addition, in the present specification, a numerical value rangeexpressed using “to” means a range that includes the preceding andsucceeding numerical values of “to” as the lower limit value and theupper limit value, respectively.

Moreover, in the present invention, a reference to “preparation” ismeant to encompass delivering a predetermined material by purchases orthe like, in addition to comprising specific materials by synthesis,combination, or the like.

Incidentally, in the present invention, “ppm” means “parts-per-million(10⁻⁶)”, “ppb” means “parts-per-billion (10⁻⁹)”, “ppt” means“parts-per-trillion (10⁻¹²)”, and “ppq” means “parts-per-quadrillion(10⁻¹⁵)”.

Moreover, in the present invention, 1 Å (angstrom) corresponds to 0.1nm.

In addition, in the notation of a group (atomic group) in the presentinvention, in a case where the group is noted without specifying whetherit is substituted or unsubstituted, the group includes both a grouphaving no substituent and a group having a substituent within a rangenot interfering with the effects of the present invention. For example,a “hydrocarbon group” includes not only a hydrocarbon group having nosubstituent (an unsubstituted hydrocarbon group) but also a hydrocarbongroup having a substituent (a substituted hydrocarbon group). This alsoapplies to each of compounds.

In the present specification, the pH of the treatment liquid is a valuemeasured by F-51 (trade name) manufactured by Horiba Ltd. at roomtemperature (25° C.).

In addition, a “radiation” in the present invention means, for example,a bright line spectrum of a mercury lamp, far ultraviolet rays typifiedby an excimer laser, extreme ultraviolet rays (EUV light), X-rays,electron beams, or the like. Incidentally, in the present invention,light means actinic rays or radiation. Unless otherwise specified,“exposure” in the present invention includes not only exposure with amercury lamp, far ultraviolet rays typified by an excimer laser, X-rays,EUV light, or the like but also writing by particle rays such aselectron beams and ion beams.

[Treatment Liquid]

The treatment liquid of an embodiment of the present invention is

a treatment liquid for a semiconductor device, containing

one or more hydroxylamine compounds selected from the group consistingof hydroxylamine and a hydroxylamine salt,

an organic basic compound,

an alcohol-based solvent, and

a surfactant,

in which a content of the alcohol-based solvent is 40% to 85% by masswith respect to the total mass of the treatment liquid, and

a pH is 8 or higher.

By allowing the treatment liquid of the embodiment of the presentinvention to have the above-mentioned configuration, the temporalstability of the residue removal performance is excellent and theanticorrosion performance for an object to be treated is excellent.

A reason therefor is not clear in detail, but is considered to be asfollows by the present inventors.

That is, the present inventors consider that a predetermined amount ofan alcohol content in the treatment liquid keeps the residue removalperformance of the treatment liquid above a certain level, andsuppresses a temporal deterioration of the residue removal performanceof the treatment liquid due to the decomposition of the hydroxylamine.They consider that by incorporation of a surfactant, the anticorrosionperformance for an object to be treated (in particular, a metal layerincluding W or Co) is improved. In addition, the present inventorsconsider that the residue removal performance of the treatment liquid isalso improved by setting a pH to be above a predetermined value.

Moreover, the treatment liquid of the embodiment of the presentinvention has an excellent defect suppression property, which enablesthe suppression of generation of defects in the object to be treated.

Hereinafter, the respective components included in the treatment liquidof the embodiment of the present invention will be described.

<Hydroxylamine Compound>

The treatment liquid of the embodiment of the present invention containsat least one or more hydroxylamine compounds selected from the groupconsisting of hydroxylamine and a hydroxylamine salt. The hydroxylaminecompound has a function of accelerating decomposition and solubilizationof the residues.

Here, the “hydroxylamine” with regard to the hydroxylamine compound ofthe treatment liquid of the embodiment of the present invention refersto a hydroxylamine compound in a broad sense including a substituted orunsubstituted alkylhydroxylamine, and the like, any of which can be usedto obtain the effects of the present invention.

The hydroxylamine compound is not particularly limited, but preferredaspects thereof include unsubstituted hydroxylamine, a hydroxylaminederivative, and salts thereof.

The hydroxylamine derivative is not particularly limited, but examplesthereof include O-methylhydroxylamine, O-ethylhydroxylamine,N-methylhydroxylamine, N,N-dimethylhydroxylamine,N,O-dimethylhydroxylamine, N-ethylhydroxylamine,N,N-diethylhydroxylamine, N,O-diethylhydroxylamine,O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, andN,N-disulfoethylhydroxylamine.

The salt of the unsubstituted hydroxylamine or the hydroxylaminederivative is preferably an inorganic acid salt or organic acid salt ofthe above-mentioned unsubstituted hydroxylamine or hydroxylaminederivative, more preferably a salt of an inorganic acid formed bybonding a non-metal atom such as Cl, S, N, and P to a hydrogen atom, andstill more preferably a salt of an acid thereof with any acid ofhydrochloric acid, sulfuric acid, or nitric acid. Among those,hydroxylamine nitrate, hydroxylamine sulfate, hydroxylaminehydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylaminesulfate, N,N-diethylhydroxylamine nitrate, or a mixture thereof ispreferable.

In addition, organic acid salts of the above-mentioned unsubstitutedhydroxylamine or hydroxylamine derivative can also be used, and examplesthereof include hydroxylammonium citrate, hydroxylammonium oxalate, andhydroxylammonium fluoride.

Among those, the hydroxylamine or the hydroxylamine sulfate ispreferable, and from the viewpoint that the defect suppression propertyand the temporal stability of the treatment liquid are more excellent,the hydroxylamine is preferable.

The content of the hydroxylamine compound is, for example, 0.1% to 30%by mass with respect to the total mass of the treatment liquid.

Among those, the content of the hydroxylamine compound is preferably 1%by mass or more, more preferably 3% by mass or more, and still morepreferably 6% by mass or more with respect to the total mass of thetreatment liquid, from the viewpoint that the residue removal propertyand the defect suppression property of the treatment liquid are moreexcellent.

In addition, the content of the hydroxylamine compound is preferably 20%by mass or less, more preferably 15% by mass or less, and still morepreferably 12% by mass or less with respect to the total mass of thetreatment liquid, from the viewpoint that the anticorrosion property ismore excellent.

The hydroxylamine compounds may be used singly or in combination of twoor more kinds thereof. In a case where the two or more kinds of thehydroxylamine compounds are used, a total content thereof is preferablywithin the range.

In addition, the content of the hydroxylamine compound with respect tothe content of a surfactant which will be described later is preferably1 or more, more preferably 10 or more, still more preferably 80 or more,and especially preferably 120 or more in terms of a mass ratio (thecontent of the hydroxylamine compound/the content of the surfactant)from the viewpoint that the residue removal property and the defectsuppression property are more excellent.

The mass ratio is preferably 10,000 or less, more preferably 2,500 orless, and still more preferably 1,000 or less from the viewpoint thatthe residue removal property, the defect suppression property, theanticorrosion property, and the temporal stability of the treatmentliquid are more excellent.

<Organic Basic Compound>

The treatment liquid of the embodiment of the present invention furtherincludes an organic basic compound in addition to the above-mentionedcomponents.

Furthermore, the organic basic compound as mentioned herein is acompound which is different from the above-mentioned hydroxylaminecompound. That is, the hydroxyamine compound is not included in theorganic basic compound.

As the organic basic compound, at least one selected from the groupconsisting of amine compounds different from the hydroxylamine compound,and a quaternary ammonium hydroxide salt is preferable.

In addition, as the organic basic compound, a cyclic compound (compoundhaving a cyclic structure) is preferable. Examples of the cycliccompound include an amine compound having a cyclic structure which willbe described later.

As the amine compound, an amine compound having a cyclic structure ispreferable from the viewpoint that it can more effectively suppress thecorrosion of a metal layer (preferably a metal layer including W and/orCo) on the substrate while ensuring residue removal performance.

In the amine compound having a cyclic structure, the amino group may bepresent in either the cyclic structure or outside the cyclic structure,or may be present in both. It should be noted that in a case where theamino group is a tertiary amino group, it is also preferable that thetertiary amino group is present in the cyclic structure and the cyclicstructure is a non-aromatic cyclic structure (nitrogen-containingnon-aromatic ring).

Examples of the amine compound include tetrahydrofurfurylamine,N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]-7-undecene,1,4-diazabicyclo[2.2.2]octane, hydroxyethylpiperazine, piperazine,2-methylpiperazine, trans-2,5-dimethylpiperazine,cis-2,6-dimethylpiperazine, 2-piperidinemethanol, cyclohexylamine,1,5-diazabicyclo[4,3,0]-5-nonene, diethylenetriamine,triethylenetetramine, and tetraethylenepentamine.

Among those, tetrahydrofurfurylamine, N-(2-aminoethyl)piperazine,1,8-diazabicyclo[5.4.0]-7-undecene, or 1,4-diazabicyclo[2.2.2]octane ispreferable as the amine compound from the viewpoint of more effectivelysuppressing the corrosion of a metal layer (preferably a metal layerincluding Co or a Co alloy) on a substrate while ensuring the residueremoval performance.

The molecular weight of the amine compound is preferably 50 to 500, morepreferably 75 to 400, and still more preferably 100 to 300.

(Tertiary Amine Compound)

It is also preferable that the treatment liquid of the embodiment of thepresent invention contains a tertiary amine compound as the aminecompound. The tertiary amine compound is a compound having a tertiaryamino group. It should be noted that the tertiary amino group containedin the tertiary amine compound is preferably a tertiary amino groupother than a tertiary amino group contained in the nitrogen-containingnon-aromatic ring. For example, N-(2-aminoethyl)piperazine is a compoundwhich is not contained in the tertiary amine compound.

Furthermore, the tertiary amine compound may have a tertiary amino groupcontained in the nitrogen-containing non-aromatic ring, and a tertiaryamino group not contained in the nitrogen-containing non-aromatic ring.

In a case where the treatment liquid contains a tertiary amine compound,it is also preferable that the treatment liquid further contains anorganic basic compound other than the tertiary amine compound.

Examples of the tertiary amine compound include trimethylamine,pyridine,N,N-dimethyl-2-[2-[4-[2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethanamine,dimethylstearylamine, and 4-amino-2-methylquinoline.

The content of the tertiary amine compound is preferably 1 ppt by massto 5 ppm by mass, more preferably 5 ppt by mass to 100 ppb by mass, andstill more preferably 50 ppt by mass to 100 ppb by mass with respect tothe total mass of the treatment liquid, from the viewpoint where thedefect suppression property is more excellent.

(Quaternary Ammonium Hydroxide Salt)

Examples of the quaternary ammonium hydroxide salt include a compoundrepresented by Formula (a1).

In Formula (a1), R^(a1) to R^(a4) each independently represent an alkylgroup having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbonatoms, an aralkyl group having 7 to 16 carbon atoms, or a hydroxyalkylgroup having 1 to 16 carbon atoms. At least two of R^(a1), . . . , orR^(a4) may be bonded to each other to form a cyclic structure, and inparticular, at least one of a combination of R^(a1) and R^(a2) or acombination of R^(a3) and R^(a4) may be bonded to each other to form acyclic structure.

Among the compounds represented by Formula (a1), at least one selectedfrom the group consisting of tetramethylammonium hydroxide,benzyltrimethylammonium hydroxide, tetrabutylammonium hydroxide,tetraethylammonium hydroxide, tetrapropylammonium hydroxide,methyltripropylammonium hydroxide, methyltributylammonium hydroxide,ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide,hexadecyltrimethylammonium hydroxide, (2-hydroxyethyl)trimethylammoniumhydroxide, and spiro-(1,1′)-bipyrrolidinium hydroxide is preferable fromthe viewpoint of easy availability. Among those, tetramethylammoniumhydroxide, tetrabutylammonium hydroxide, or benzyltrimethylammoniumhydroxide is more preferable.

The molecular weight of the quaternary ammonium hydroxide salt ispreferably 90 to 400, more preferably 90 to 300, and still morepreferably 90 to 260.

The organic basic compounds may be used singly or in combination of twoor more kinds thereof.

The content of the organic basic compound (a total content in a casewhere two or more kinds of the organic basic compounds are used; forexample, in a case where the treatment liquid contains theabove-mentioned tertiary amine compound and an organic basic compoundother than the tertiary amine compound, a total content thereof) is, forexample, 1 ppt by mass to 20% by mass, preferably 0.1% to 20% by mass,more preferably 0.5% to 5% by mass, and still more preferably 0.5% to1.5% by mass with respect to the total mass of the treatment liquid.

In addition, the content of the organic basic compound with respect tothe content of the surfactant which will be described later ispreferably 1 to 150, more preferably 5 to 125, and still more preferably5 or more and less than 118 in terms of a mass ratio (the content of theorganic basic compound/the content of the surfactant) from the viewpointthat the residue removal property, the defect suppression property, theanticorrosion property, and the temporal stability are more excellent.

<Surfactant>

The treatment liquid of the embodiment of the present invention furthercontains a surfactant, in addition to the above-mentioned components.

The type of the surfactant is not particularly limited, a knownsurfactant can be used, and examples thereof include an ionic surfactant(for example, an anionic surfactant, a cationic surfactant, and anamphoteric surfactant), a nonionic surfactant (for example, a nonionicsurfactant, a silicone-based surfactant, and a fluorine-basedsurfactant).

Examples of the anionic surfactant include aromatic sulfonic acid-basedsurfactants such as alkylbenzene sulfonates (dodecylbenzene sulfonicacid and the like) and alkyldiphenyl ether sulfonates (dodecyldiphenyloxide sulfonate and the like), monosoap-based anionic surfactants, ethersulfate-based surfactants, phosphate-based surfactants, and carboxylicacid-based surfactants.

Examples of the cationic surfactant include amine salts (alkylaminesalts such as an octadecylamine salt, a chlorhexidine salt, and thelike, preferably hydrochlorides such as chlorhexidine dihydrochlorideand octadecylamine hydrochloride), pyridinium salts (preferably halidesalts such as cetylpyridinium chloride, dodecylpyridinium chloride, anddequalinium chloride), and quaternary ammonium salts (preferably halidesalts, preferably having a molecular weight of 260 or more, and morepreferably having a molecular weight of more than 260, such asbenzalkonium chloride, cetyltrimethylammonium bromide, benzethoniumchloride, distearyldimethylammonium chloride, anddodecyltrimethylammonium chloride).

Examples of the amphoteric surfactant include alkyl betaine-basedsurfactants (2-alkyl-n-carboxymethyl-n-hydroxyethyl imidazoliniumbetaine and the like), amine oxide-based surfactants, and fatty acidamide propyl betaines (cocamidopropyl betaine and lauramidopropylbetaine).

Examples of the nonionic surfactant include sugar ester-basedsurfactants such as sorbitan fatty acid ester and polyoxyethylenesorbitan fatty acid ester, alkylglycoside-based surfactants such aslauryl glucoside, fatty acid ester-based surfactants such aspolyoxyethylene resin acid ester and polyoxyethylene fatty acid diethyl,and ether-based surfactants such as polyoxyethylene alkyl ethers(polyoxyethylene lauryl ether and the like), polyoxyethylene alkylphenylethers (octylphenol ethoxylate and the like), andpolyoxyethylene/polypropylene glycol.

Among those, as the surfactant, the cationic surfactant is preferable.Further, the cationic surfactant preferably contains a quaternarynitrogen atom. The quaternary nitrogen atom is contained in, forexample, a quaternary ammonium salt or a pyridinium salt. It should benoted that the cationic surfactant containing a quaternary nitrogen atomis preferably different from the quaternary ammonium hydroxide salt (forexample, the compound represented by Formula (a1)) mentioned in thedescription of the organic basic compound.

From the viewpoint that the defect suppression property, the residueremoval property, and the temporal stability of the treatment liquid aremore excellent, the lower limit of the content of the surfactant ispreferably 1 ppm by mass or more, more preferably 85 ppm by mass ormore, still more preferably 0.01% by mass or more, and particularlypreferably 0.05% by mass or more with respect to the total mass of thetreatment liquid. The upper limit is preferably 2% by mass or less, morepreferably 1% by mass or less, and still more preferably 0.5% by mass orless.

Furthermore, it is also preferable that the content of the surfactantsatisfies preferred ranges of the mass ratio of the content of thehydroxylamine compound to the content of the surfactant, and/or the massratio of the content of the organic basic compound to the content of thesurfactant, as described above.

The surfactants may be used singly or in combination of two or morekinds thereof. In a case where the two or more kinds of thehydroxylamine compounds are used, a total content thereof is preferablywithin the range.

<Alcohol-Based Solvent>

The treatment liquid of the embodiment of the present invention furthercontains an alcohol-based solvent, in addition to the above-mentionedcomponents.

The alcohol-based solvent is preferably a water-soluble alcohol-basedsolvent.

Examples of the alcohol-based solvent include an alkane diol, analkylene glycol, alkoxyalcohol, a saturated aliphatic monohydricalcohol, an unsaturated non-aromatic monohydric alcohol, and a trihydricor higher alcohol.

Examples of the alkanediol include glycol, 2-methyl-1,3-propanediol,1,2-propanediol, 1,3-propanediol (1,3-dihydroxypropane),2-methyl-2,4-pentanediol, 2,2-dimethyl-1,3-hexanediol, 1,4-butanediol(1,4-dihydroxybutane), 1,3-butanediol, 1,2-butanediol, 2,3-butanediol,2,5-dihydroxy-2,5-dimethylhexane, pinacol, and alkylene glycol.

Examples of the alkylene glycol include ethylene glycol, propyleneglycol, diethylene glycol, dipropylene glycol, triethylene glycol, andtetraethylene glycol.

Examples of the alkoxyalcohol include 3-methoxy-3-methyl-1-butanol,3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, 1-methoxy-2-butanol, andglycol monoether.

Examples of the glycol monoether include ethylene glycol monomethylether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propylether, ethylene glycol monoisopropyl ether, ethylene glycol monobutylether, diethylene glycol monomethyl ether, diethylene glycol monoethylether, diethylene glycol monobutyl ether, triethylene glycol monomethylether, triethylene glycol monoethyl ether, triethylene glycol monobutylether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol,2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropyleneglycol monomethyl ether, dipropylene glycol monoethyl ether, dipropyleneglycol mono-n-propyl ether, tripropylene glycol monoethyl ether,tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether,and diethylene glycol monobenzyl ether.

Examples of the saturated aliphatic monohydric alcohol include methanol,ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol,isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, and1-hexanol.

Examples of the unsaturated non-aromatic monohydric alcohol includeallyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol,and 4-penten-2-ol.

Examples of the low-molecular-weight alcohol including a ring structureinclude tetrahydrofurfuryl alcohol, furfuryl alcohol, and1,3-cyclopentanediol.

Examples of the trihydric or higher alcohol include glycerin.

Among those, the alcohol-based solvent is preferably an alkoxyalcoholcontaining an alkoxy group. The alkoxy group is preferably an alkoxygroup having 1 to 6 carbon atoms, such as a methoxy group, an ethoxygroup, a propoxy group, and a butoxy group.

The molecular weight of the alcohol-based solvent is preferably 32 to250, more preferably 40 to 200, and still more preferably 50 to 150.

The content of the alcohol-based solvent is 40% to 85% by mass withrespect to the total mass of the treatment liquid, and from theviewpoint that the anticorrosion property and the temporal stability aremore excellent, the content is preferably 50% by mass or more, and stillmore preferably 60% by mass or more. The content is preferably 80% bymass or less, and more preferably 70% by mass or less from the viewpointthat the defect suppression property and the residue removal propertyare more excellent.

The alcohol-based solvents may be used singly or in combination of twoor more kinds thereof. In a case where the two or more kinds of thehydroxylamine compounds are used, a total content thereof is preferablywithin the range.

<Alkyl Halide Compound>

The treatment liquid of the embodiment of the present inventionpreferably further contains an alkyl halide compound, in addition to theabove-mentioned components.

By incorporating the alkyl halide compound, the defect suppressionproperty of the treatment liquid is more excellent. The alkyl halidecompound is not limited as long as it has an alkyl halide group.

Among those, the number of halogen atoms (preferably chlorine atoms)contained in the alkyl halide compound is preferably 1 to 10, and morepreferably 1 or 2. The alkyl halide compound preferably has ahydrocarbon group except for the halogen atom portion.

The content of the alkyl halide compound is preferably 1 ppt by mass to5 ppm by mass, and more preferably 50 ppt by mass to 100 ppb by masswith respect to the total mass of the treatment liquid, from theviewpoint that the defect suppression property is more excellent.

<Reducing Agent>

The treatment liquid of the embodiment of the present inventionpreferably further contains a reducing agent, in addition to theabove-mentioned components.

By incorporating the reducing agent, the residue removal property andthe temporal stability of the treatment liquid are more excellent.

In addition, the reducing agent does not include a hydroxylaminecompound.

The reducing agent is preferably a reducing substance such as a compoundhaving an OH group or a CHO group, or a compound containing a sulfuratom. The reducing agent has an oxidizing action and has a function ofoxidizing OH⁻ ions, dissolved oxygen, and the like which causedecomposition of the hydroxylamine compound.

Examples of the reducing agent include a compound represented by (B)below.

In Formula (B), R^(1B) to R^(5B) each independently represent a hydrogenatom, a hydroxyl group, or a hydrocarbon group which may have aheteroatom. Further, in a case where R^(1B) to R^(5B) each have ahydrocarbon group which may have a heteroatom, the hydrocarbon group mayhave a substituent.

In Formula (B), examples of the hydrocarbon group represented by each ofR^(1B) to R^(5B) which may have a heteroatom include a hydrocarbon groupand a hydrocarbon group having a heteroatom.

Examples of the hydrocarbon group represented by each of R^(1B) toR^(5B) include an alkyl group (preferably having 1 to 12 carbon atoms,and more preferably having 1 to 6 carbon atoms) and an alkenyl group(preferably having 2 to 12 carbon atoms, and more preferably having 2 to6 carbon atoms), an alkynyl group (preferably having 2 to 12 carbonatoms, and more preferably having 2 to 6 carbon atoms), an aryl group(preferably having 6 to 22 carbon atoms, more preferably having 6 to 14carbon atoms, and still more preferably having 6 to 10 carbon atoms),and an aralkyl group (preferably having 7 to 23 carbon atoms, morepreferably having 7 to 15 carbon atoms, and still more preferably having7 to 11 carbon atoms).

In addition, examples of the hydrocarbon group having a heteroatom,represented by each of R^(1B) to R^(5B), include the hydrocarbon groupin which —CH₂— is substituted with any one selected from the groupconsisting of —O—, —S—, —CO—, —SO₂—, and —NR^(a)—, or a divalent groupformed by combination of a plurality of these groups. R^(a) represents ahydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms(preferably an alkyl group having 1 to 5 carbon atoms).

Moreover, examples of the substituent include a hydroxyl group, acarboxyl group, or a substituted or unsubstituted amino group (as thesubstituent, an alkyl group having 1 to 6 carbon atoms is preferable,and an alkyl group having 1 to 3 carbon atoms is more preferable).

The compound represented by Formula (B) preferably has two or morehydroxyl groups, and more preferably has two or three or more hydroxylgroups. The position at which the hydroxyl group is substituted is notparticularly limited, but among these, R^(1B) and/or R^(2B) ispreferable.

Examples of the compound represented by Formula (B) include catechol,resorcinol, isoeugenol, o-methoxyphenol,4,4′-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate,methyl salicylate, and 2,6-di-t-butyl-p-cresol.

Among those, catechol is preferable as the compound represented byFormula (B).

Moreover, a catechol derivative is also preferable as the reducingagent.

Examples of the catechol derivative include dopamine, 3-methylcatechol,4-methylcatechol, catechol-4-acetic acid, noradrenaline, adrenaline,3-(3,4-dihydroxyphenyl)-L-alanine, 5,6-dihydroxyindole, catechin,isoflavone, gallic acid, ellagic acid, 4-tert-butylpyrocatechol,pyrogallol, 5-sec-butylpyrogallol, 4-phenylpyrogallol,4-methyl-1,2,3-benzenetriol, 4,5,6-trichloropyrogallol,4,5,6-trimethylpyrogallol, 4,5-dimethylpyrogallol, and4,6-dimethylpyrogallol.

As the reducing agent, ascorbic acid is also preferable.

Furthermore, examples of the ascorbic acid include ascorbic acids suchas ascorbic acid, isoascorbic acid, ascorbic acid sulfuric ester,ascorbic acid phosphoric ester, ascorbic acid 2-glucoside, ascorbylpalmitic ester, ascorbyl tetraisopalmitate, ascorbic acid isopalminate,and salts thereof, and the ascorbic acid is preferable.

A compound containing a sulfur atom is also preferable as the reducingagent.

Furthermore, examples of the compound containing a sulfur atom includemercaptosuccinic acid, dithiodiglycerol [S(CH₂CH(OH)CH₂(OH))₂],bis(2,3-dihydroxypropylthio)ethylene [CH₂CH₂(SCH₂CH(OH)CH₂(OH))₂],sodium 3-(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate[CH2(OH)CH(OH)CH₂SCH₂CH(CH₃)CH₂SO₃Na], 1-thioglycerol[HSCH₂CH(OH)CH₂(OH)], sodium 3-mercapto-1-propanesulfonate[HSCH₂CH₂CH2SO₃Na], 2-mercaptoethanol [HSCH₂CH₂(OH)], thioglycolic acid[HSCH₂CO₂H], and 3-mercapto-1-propanol [HSCH₂CH₂CH₂OH]. Among these, acompound having a SH group (mercaptan compound) is preferable, and1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol,3-mercapto-1-propanol, or thioglycolic acid is more preferable, and1-thioglycerol or thioglycolic acid is still more preferable.

Among those, the reducing agent is preferably one or more reducingagents selected from the group consisting of catechol and a derivativethereof, and a mercaptan compound.

The content of the reducing agent is preferably 0.01% to 5% by mass,more preferably 0.05% to 3% by mass, and still more preferably 0.1% to1% by mass with respect to the total mass of the treatment liquid.

<Acetic Acid>

The treatment liquid of the embodiment of the present inventionpreferably further contains acetic acid.

By incorporating the acetic acid, the defect suppression property of thetreatment liquid is more excellent.

The content of the acetic acid is preferably 1 ppt by mass to 0.1% bymass, more preferably 500 ppt by mass to 0.09% by mass, and still morepreferably 5 ppb by mass to 0.08% by mass with respect to the total massof the treatment liquid.

<Other Organic Acids>

The treatment liquid of the embodiment of the present inventionpreferably further contains another organic acid, in addition to theabove-mentioned components.

By incorporating other organic acid, the residue removal property of thetreatment liquid and the temporal stability are more excellent.

Such another organic acid is, for example, a component different fromthe above-mentioned acetic acid and reducing agent.

Such another organic acid preferably has one or more acid groups, andthe acid group of such another organic acid is preferably at least onefunctional group selected from a carboxylic acid group, a sulfonic acidgroup, and a phosphonic acid group, with the carboxylic acid group beingmore preferable.

Specific examples of other organic acids include polyaminopolycarboxylicacids, aliphatic dicarboxylic acids, and aliphatic polycarboxylic acidscontaining a hydroxyl group.

The polyaminopolycarboxylic acid is a compound having a plurality ofamino groups and a plurality of carboxylic acid groups, and examplesthereof include a monoalkylenepolyamine polycarboxylic acid, apolyalkylenepolyamine polycarboxylic acid, a polyaminoalkanepolycarboxylic acid, a polyaminoalkanol polycarboxylic acid, and ahydroxyalkyl ether polyamine polycarboxylic acid.

Examples of the aliphatic dicarboxylic acids include oxalic acid,malonic acid, succinic acid, and maleic acid, and the oxalic acid, themalonic acid, or the succinic acid is preferable.

Examples of the aliphatic polycarboxylic acid including a hydroxyl groupinclude malic acid, tartaric acid, and citric acid, and the citric acidis preferable.

The content of such another organic acid is preferably 0.01% to 5% bymass, more preferably 0.05% to 3% by mass, and still more preferably0.1% to 1% by mass with respect to the total mass of the treatmentliquid.

<Metal-Containing Particles>

The treatment liquid of the embodiment of the present invention mayfurther contain metal-containing particles containing one or more metalcomponents selected from the group consisting of Na, Ca, Fe, and Cr.

Furthermore, the metal-containing particles have a particle diameter of0.02 to 0.05 μm.

The diameter and the content of such metal-containing particles in thetreatment liquid are, for example, Agilent 8900 triple quadrupoleSNP-ICP/MS (small nanoparticle-inductively coupled plasma massspectrometry, Option #200 for semiconductor analysis) can be used forthe measurement.

The metal-containing particle contains one or more metal componentsselected from the group consisting of Na, Ca, Fe, and Cr, and in a casewhere the particle diameter is within a predetermined range, thestructure is not particularly limited, and for example, the metal may bea simple substance or an alloy, or may be associated with a componentother than the metal.

The content of the metal-containing particles is preferably 10 ppt bymass to 10 ppb by mass with respect to the total mass of the treatmentliquid from the viewpoint that the defect suppression property of thetreatment liquid is more excellent.

By setting the content of the metal-containing particles to 10 ppb bymass or less, it is possible to prevent the particles from remaining onthe substrate to cause scratches.

On the other hand, by setting the content of the metal-containingparticles to 10 ppt by mass or more, the residue of the ionic metal canbe reduced.

The metal-containing particles are often contained as impurities in theraw material of the treatment liquid, and in a case where the unpurifiedraw materials are mixed, an amount exceeding the preferable range isoften brought into the treatment liquid. Therefore, by subjecting a partor all of the raw materials constituting the treatment liquid to apurification treatment such as filtering before or after mixing, thecontent of the metal-containing particles in the finally obtainedtreatment liquid can be adjusted to a predetermined range.

In addition, the metal-containing particles may be added separately inpreparation of treatment liquid.

<Water>

The treatment liquid of the embodiment of the present inventionpreferably contains water.

The content of water in the treatment liquid of the embodiment of thepresent invention is not particularly limited and is, for example, 15%to 59.999% by mass with respect to the total mass of the treatmentliquid.

<pH (pH Adjusting Agent)>

The pH of the treatment liquid of the embodiment of the presentinvention is 8 or more. By setting the pH of the treatment liquid to bein the alkaline range, the residue removal performance is excellent.

Among those, the pH of the treatment liquid is preferably 9 or more,more preferably 10 or more, and still more preferably higher than 10from the viewpoints that the anticorrosion property against Co, thedefect suppression property, and the residue removal property are moreexcellent.

In addition, the pH of the treatment liquid is preferably 14 or less,more preferably 12 or less, and still more preferably less than 12 fromthe viewpoint that the anticorrosion property against W and the defectsuppression property are more excellent.

In order to adjust the treatment liquid to be in the pH range, thetreatment liquid may include a pH adjusting agent. The above-mentionedorganic basic compound may also serve as the pH adjusting agent forincreasing the pH of the treatment liquid.

Examples of the pH adjusting agent for increasing the pH of thetreatment liquid include 1,8-diazabicyclo [5.4.0]-7-undecene (DBU),tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide(TBAH), and an inorganic base (KOH and the like). In a case where aninorganic base is used as the pH adjusting agent, the amount of theinorganic base is preferably 0.1% by mass or less with respect to thetotal mass of the treatment liquid.

The acid as described above (acetic acid, another organic acid, and thelike) may also serve as a pH adjusting agent for lowering the pH of thetreatment liquid.

Examples of the pH adjusting agent for lowering the pH of the treatmentliquid include inorganic acids (HCl, H₂SO₄, H₃PO₄, and the like) andcitric acid.

<Other Additives>

Examples of other additives include an organic solvent other than analcohol, an anticorrosive material, an antifoaming agent, a rustinhibitor, and a preservative.

<Metal Concentration>

In the treatment liquid of the embodiment of the present invention, itis preferable that the ion concentration of the metals (metal elementsof Co, K, Cu, Mg, Mn, Li, Al, Ni, and Zn) contained as impurities in theliquid is 5 ppm by mass or less (preferably 1 ppm by mass or less). Inparticular, in a view that high-purity treatment liquids are furtherdemanded in the manufacture of state-of-the-art semiconductor elements,it is more preferable that the metal concentration is less than a valuein a ppm-by-mass order, that is, a value in a ppb-by-mass order or less,it is still more preferable that the metal concentration is in appt-by-mass order, and it is particularly preferable that the metal isnot substantially included.

Examples of a method for sufficiently reducing the metal concentrationinclude performing distillation or filtration using an ion exchangeresin in at least one of a stage using raw materials used in theproduction of a treatment liquid or a stage after preparation of thetreatment liquid.

Examples of a method other than the method for reducing the metalconcentration include a use of a container having little elution ofimpurities as shown in the section describing a container housing thetreatment liquid with regard to a “container” housing raw materials usedin the production of a treatment liquid. Other examples of the methodinclude a method of carrying out lining of a fluorine-based resin for aninner wall of a “pipe” so as to prevent the elution of metal fractionsfrom the pipe or the like during the preparation of the treatmentliquid.

<Applications>

The treatment liquid of the embodiment of the present invention is atreatment liquid for a semiconductor device. In the present invention,the expression, “for a semiconductor device”, means a use for themanufacture of a semiconductor device. The treatment liquid of theembodiment of the present invention can also be used in any steps formanufacturing a semiconductor device, and can also be used in, forexample, a treatment of an insulating film, a resist, or anantireflection film, which is present on a substrate, a treatment of dryetching residues (residues of a photoresist film, residues of a metalhard mask, and the like), a treatment of ashing residues, and the like.

With regard to more specific applications of the treatment liquid, thetreatment liquid is used as a pre-wet liquid applied on a substrate inorder to improve the coatability of an actinic ray-sensitive orradiation-sensitive composition before a step of forming a photoresistfilm using the composition; a cleaning liquid used for removing residuessuch as dry etching residues, or the like; a solution (for example, aremoving liquid and a peeling liquid) used for removing various resistfilms (preferably a photoresist film) used for the formation of apattern; and a solution (for example, a removing liquid and a peelingliquid) used for removing a permanent film (for example, a color filter,a transparent insulating film, and a resin-made lens) or the like from asubstrate. In addition, the treatment liquid can also be used as adeveloper for various actinic ray-sensitive or radiation-sensitive resincomposition layers for pattern formation.

In addition, the treatment liquid can also be used as a cleaning liquidwhich is used for removing residues such as metal impurities and fineparticles from a substrate after chemical mechanical polishing. Thesubstrate after the removal of a permanent film may be used again in ause of a semiconductor device, and therefore, the removal of thepermanent film is included in the step of manufacturing a semiconductordevice.

The treatment liquid may be used as an etching liquid for treating themetal layer of the substrate having a metal layer.

Among the applications, the treatment liquid can also be suitably usedas a cleaning liquid for removing dry etching residues, a solution forremoving various resist films used for pattern formation, or a cleaningliquid for removing residues such as metal impurities and fine particlesfrom a substrate after chemical mechanical polishing.

The treatment liquid of the embodiment of the present invention may beused only in one or two or more of the applications.

As miniaturization and high functionalization of semiconductor devicesproceed in recent years, metals used for wiring materials, plugmaterials, or the like are required to be more electrically conductive.For example, it is presumed that substitution of aluminum (Al) andcopper (Cu) in the metals used as the wiring materials with cobalt (Co)proceeds. In addition, it is expected that in addition to tungsten (W)in the metals used as the plug materials, a demand for Co increases.

Therefore, it is preferable that the treatment liquid has a small amountof corrosion with respect to W and Co.

The treatment liquid of the embodiment of the present invention ispreferably used for a treatment of a substrate having a metal layercontaining one or more selected from the group consisting of W and Co.Further, the treatment liquid of the embodiment of the present inventionis preferably used as a treatment liquid for manufacturing asemiconductor device including a substrate having a metal layercontaining one or more selected from the group consisting of W and Co.

In addition, the metal layer containing one or more selected from thegroup consisting of W and Co may be a metal layer consisting of W and/orCo, or a metal layer which is an alloy including W and/or Co, or mayalso be another form of the metal layer including W and/or Co.

[Method for Producing Treatment Liquid]

<Liquid Preparing Method for Treatment Liquid>

The treatment liquid can be produced by a known method.

Hereinafter, the method for producing the treatment liquid will bedescribed in detail.

(Step of Purifying Raw Materials)

In the production of the treatment liquid, it is preferable to purifyany one or more of the raw materials for preparing the treatment liquidby distillation, ion exchange, filtration or the like in advance. As forthe degree of purification, for example, it is preferable to purify theraw materials to have a purity of 99% or more, and more preferable tohave a purity of 99.9% or more.

The purification method is not particularly limited, but examplesthereof include a method including passing through an ion exchangeresin, an reverse osmosis (RO) membrane, or the like, and a method ofdistillation, filtering which will be described later, or the like.Specific examples of the method include a method in which a primarypurification is performed by passage through a reverse osmosis membraneor the like, and then a secondary purification is carried out by passagethrough a purification device including a cation exchange resin, ananion exchange resin, or a mixed bed ion exchange resin.

Incidentally, for the purification treatment, a plurality of theabove-mentioned known purification methods may be carried out incombination.

In addition, the purification treatments may be carried out a pluralityof times.

(Filtering)

The filter is not particularly limited as long as it is a filter whichhas been used in filtering applications or the like from the relatedart. Examples thereof include a filter formed with a fluorine resin suchas polytetrafluoroethylene (PTFE) and atetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), apolyamide-based resin such as nylon, and a polyolefin resin (including ahigh-density polyolefin and an ultrahigh-molecular-weight polyolefin)such as polyethylene and polypropylene (PP), or the like. Among thesematerials, a material selected from the group consisting of thepolyethylene, the polypropylene (including a high-densitypolypropylene), the fluorine resin such as PTFE and PFA, and thepolyamide-based resin such as nylon is preferable, and among these, afilter with a fluorine resin such as PTFE and PFA is more preferable. Byusing a filter formed with these materials, high-polarity foreignmatters which are likely to cause defects can be more effectivelyremoved.

The critical surface tension of the filter is preferably 70 mN/m ormore, more preferably 95 mN/m or less, and still more preferably from 75mN/m to 85 mN/m. Further, the value of the critical surface tension is anominal value of a manufacturer. By using a filter having a criticalsurface tension in the range, high-polarity foreign matters which arelikely to cause defects can be more effectively removed.

The pore diameter of the filter is preferably approximately 2 to 20 nm,and more preferably 2 to 15 nm. By adjusting the pore diameter of thefilter to be in the range, it is possible to reliably remove fineforeign matters such as impurities and aggregates included in the rawmaterials while suppressing clogging in filtering.

In a case of using filters, different filters may be combined. In thiscase, the filtering with the first filter may be performed once or twiceor more times. In a case where the filtering is performed twice or moretimes by combining different filters, the pore diameter at the secondfiltering or later is preferably the same as or smaller than the porediameter at the first filtering. In addition, the first filters withdifferent pore diameters in the above-mentioned range may be combined.With regard to the pore diameters herein, reference can be made tonominal values of filter manufacturers. A commercially available filtermay be selected from various filters provided by Nihon Pall Ltd.,Advantech Toyo Roshi Kaisha., Ltd., Nihon Entegris K. K. (formerlyNippon Microlith Co., Ltd.), Kitz Micro Filter Corporation, or the like,for example. Further, a polyamide-made “P-Nylon Filter (pore diameter of0.02 μm, critical surface tension of 77 mN/m)”; (manufactured by NihonPall Ltd.), a high-density polyethylene-made “PE⋅Clean Filter (porediameter of 0.02 μm)”; (manufactured by Nihon Pall Ltd.), and ahigh-density polyethylene-made “PE⋅Clean Filter (pore diameter of 0.01μm)”; (manufactured by Nihon Pall Ltd.) can also be used.

As the second filter, a filter formed of the same materials as those ofthe above-mentioned first filter, and the like can be used. The porediameter of the second filter is preferably approximately 1 to 10 nm.

Moreover, in the present invention, the filtering step is preferablyperformed at room temperature (25° C.) or lower, more preferablyperformed at 23° C. or lower, and still more preferably performed at 20°C. or lower. Further, the temperature is preferably 0° C. or higher,more preferably 5° C. or higher, and still more preferably 10° C. orhigher.

In the filtering step, particulate foreign matters or impurities can beremoved, but in a case of performing the filtering at the temperature,the amounts of the particulate foreign matters and/or impuritiesdissolved in the raw materials are reduced, and therefore, they areefficiently removed by filtering.

In addition, in order to adjust the content of the metal-containingparticles in the finally obtained treatment liquid within the range asdescribed above, a part or all of the raw materials and a mixturethereof may be subjected to a purification treatment by making anadjustment so that the metal-containing particles having a constantamount and/or particle diameter remain.

(Liquid Preparing Step)

The liquid preparation for the treatment liquid of the embodiment of thepresent invention is not particularly limited, and the treatment liquidcan be produced by mixing the above-mentioned respective components, forexample. The order and/or timing for mixing the above-mentionedrespective components is not particularly limited, and examples thereofinclude a method in which a hydroxylamine compound is dispersed inadvance in water having a pH adjusted, and predetermined components aresequentially mixed.

<Kit and Concentrate>

The treatment liquid in the embodiment of the present invention may beused in the form of a kit having raw materials of the treatment liquiddivided into a plurality of parts.

Although not being particularly limited, examples of a specific methodfor using the treatment liquid in the form of the kit include an aspectin which a liquid composition containing a hydroxylamine compound and anorganic basic compound in an alcohol-based solvent is prepared as afirst liquid, and a liquid composition containing the other componentsis prepared as a second liquid.

Further, the treatment liquid may be prepared by using a concentrate. Ina case where a concentrate of the treatment liquid is prepared, theconcentration rate is appropriately determined by the composition forconstitution, but is preferably 5 to 2,000 folds. That is, the treatmentliquid is used after dilution of the concentrate to 5 to 2,000 folds. Inaddition, from the viewpoint of further improving the temporal stabilityof the residue removal performance, it is preferable to reduce the waterwhich causes the decomposition of the hydroxylamine compound as much aspossible, and thus prepare a composition including a large amount ofalcohol-based solvent.

<Container (Housing Container)>

The treatment liquid of the embodiment of the present invention can befilled in any container as long as the container does not have anyproblem such as corrosion properties (irrespective of whether thetreatment liquid is a kit or a concentrate), stored, transported, andused. As for the container, as a container used in semiconductorapplications, a container which has high cleanliness in the containerand less elution of impurities is preferable. Examples of the usablecontainer include, but are not limited to, “CLEAN BOTTLE” series(manufactured by Aicello Chemical Co., Ltd.) and “PURE BOTTLE”(manufactured by Kodama Plastics Co., Ltd.). The inner wall of thecontainer is preferably formed of one or more resins selected from thegroup consisting of a polyethylene resin, a polypropylene resin, and apolyethylene-polypropylene resin, other resins, and a metal which hasbeen antirust and metal elution preventing treatments, such as stainlesssteel, Hastelloy, Inconel, and Monel.

As such other resins, a fluorine-based resin (perfluoro resin) ispreferable. In this manner, by using a container having an inner wallformed of a fluorine-based resin, occurrence of a problem of elution ofethylene or propylene oligomers can be suppressed, as compared with acontainer having an inner wall formed of a polyethylene resin, apolypropylene resin, or a polyethylene-polypropylene resin.

Specific examples of such a container having an inner wall which is afluorine-based resin include a FluoroPurePFA composite drum manufacturedby Entegris Inc. Further, the containers described on page 4 and thelike of JP1991-502677A (JP-H03-502677A), page 3 and the like ofWO2004/016526A, pages 9 and 16 of WO99/046309A, or the like can also beused.

Moreover, for the inner wall of the container, the quartz and theelectropolished metal material (that is, the metal material which hasbeen completely electropolished) are also preferably used, in additionto the above-mentioned fluorine-based resin.

The metal material used for producing the electropolished metal materialis preferably a metal material which contains at least one selected fromthe group consisting of chromium and nickel, and has a total content ofchromium and nickel of more than 25% by mass with respect to the totalmass of the metal material, and examples thereof include stainless steeland a nickel-chromium alloy.

The total content of chromium and nickel in the metal material is morepreferably 30% by mass or more with respect to the total mass of themetal material.

In addition, the upper limit value of the total content of Cr and Ni inthe metal material is not particularly limited, but is generallypreferably 90% by mass or less.

The stainless steel is not particularly limited, and a known stainlesssteel can be used. Among those, an alloy containing 8% by mass or moreof nickel is preferable, and austenitic stainless steel containing 8% bymass or more of nickel is more preferable. Examples of the austeniticstainless steel include Steel Use Stainless (SUS) 304 (Ni content of 8%by mass, Cr content of 18% by mass), SUS 304L (Ni content of 9% by mass,Cr content of 18% by mass), SUS 316 (Ni content of 10% by mass, Crcontent of 16% by mass), and SUS 316L (Ni content of 12% by mass, Crcontent of 16% by mass).

The nickel-chromium alloy is not particularly limited and a knownnickel-chromium alloy can be used. Among those, a nickel-chromium alloyhaving a nickel content of 40% to 75% by mass and a chromium content of1% to 30% by mass is preferable.

Examples of the nickel-chromium alloy include Hastelloy (trade name,hereinafter, the same shall apply), Monel (trade name, hereinafter, thesame shall apply), and Inconel (trade name, hereinafter, the same shallapply). More specific examples thereof include Hastelloy C-276 (Nicontent of 63% by mass, Cr content of 16% by mass), Hastelloy C (Nicontent of 60% by mass, Cr content of 17% by mass), and Hastelloy C-22(Ni content of 61% by mass, Cr content of 22% by mass).

In addition, the nickel-chromium alloy may further contain boron,silicon, tungsten, molybdenum, copper, cobalt, or the like, as desired,in addition to the above-mentioned alloys.

A method for electropolishing the metal material is not particularlylimited, and a known method can be used. For example, the methodsdescribed in paragraphs [0011] to [0014] of JP2015-227501A, paragraphs[0036] to [0042] of JP2008-264929A, or the like can be used.

It is presumed that the metal material has a larger content of chromiumin the passivation layer on the surface than the content of chromium inthe parent phase by electropolishing the metal material. As a result, itis presumed that since it is difficult for the metal elements to flowinto the treatment liquid from the inner wall coated with theelectropolished metal material, it is possible to obtain a treatmentliquid having a reduced amount of metal impurities.

In addition, it is preferable that the metal material is buffed. Thebuffing method is not particularly limited, and known methods can beused. The size of the abrasive grain used to finish the buffing is notparticularly limited, but is preferably #400 or less in view that theunevenness of the surface of the metal material is likely to be smaller.

Incidentally, buffing is preferably performed before theelectropolishing.

In addition, the metal material may be subjected to a treatmentincluding one of buffing, acid cleaning, magnetic fluid polishing, andthe like or a combination of two or more thereof in a plurality of stepsthat are performed by changing the number of a size or the like of theabrasive grains.

In the present invention, the container, and the treatment liquid housedin the container may be referred to as a treatment liquid receptor insome cases.

The inside of these containers is preferably cleaned before thetreatment liquid is filled. For the liquid used for the cleaning, theamount of the metal impurities in the liquid is preferably reduced. Thetreatment liquid of the embodiment of the present invention may bebottled in a container such as a gallon bottle and a coated bottle afterthe production, transported, and stored.

In order to prevent the change in the components in the treatment liquidduring the storage, the inside of the container may be replaced withinert gas (nitrogen, argon, or the like) with a purity of 99.99995% byvolume or more. In particular, a gas having a low moisture content ispreferable. In addition, during the transportation and the storage, thetemperature may be controlled to a normal temperature in the range of−20° C. to 20° C. to prevent deterioration.

(Clean Room)

It is preferable that handlings including production of the treatmentliquid of the embodiment of the present invention, opening and/orcleaning of a housing container, filling of the treatment liquid, andthe like, treatment analysis, and measurements are all performed inclean rooms. It is preferable that the clean room satisfies 14644-1clean room standards. It is preferable that the clean room satisfies anyone of International Organization for Standardization (ISO) Class 1, ISOClass 2, ISO Class 3, or ISO Class 4, it is more preferable that theclean room satisfies ISO Class 1 or ISO Class 2, and it is still morepreferable that the clean room satisfies ISO Class 1.

[Method for Cleaning Substrate]

As one aspect of the method for cleaning a substrate using the treatmentliquid of the embodiment of the present invention, an aspect having acleaning step of using the treatment liquid to clean a substrate havinga metal layer containing one or more selected from the group consistingof W and Co (hereinafter also referred to as a “cleaning step B”) may bementioned. Further, the cleaning method of the aspect may have atreatment liquid preparing step (hereinafter referred to as a “treatmentliquid preparing step A”) of preparing the treatment liquid before thecleaning step B.

In the following description of the substrate cleaning method, a case ofperforming the treatment liquid preparing step A before the cleaningstep B is shown as an example, but the present invention is not limitedto this, and the substrate cleaning method of the present invention maybe performed using the treatment liquid that has been prepared inadvance.

<Object to Be Cleaned>

The object to be cleaned in the method for cleaning a substrateaccording to the present invention is preferably a substrate having ametal layer containing one or more selected from the group consisting ofW and Co. Examples of the object to be cleaned by the method forcleaning a substrate according to the present invention include alaminate comprising at least a metal layer containing one or moreselected from the group consisting of W and Co (hereinafter simplyreferred to as a “metal layer”), an interlayer insulating layer, and ametal hard mask in this order on the substrate. The laminate further hasholes formed toward the substrate from the surface (apertures) of themetal hard mask so as to expose the surface of the metal layer through adry etching step or the like.

A method for producing a laminate having holes as described above is notparticularly limited, but common examples thereof include a method inwhich a laminate before the treatment, having a substrate, a metallayer, an interlayer insulating layer, and a metal hard mask in thisorder, is subjected to a dry etching step using the metal hard mask as amask, and the interlayer insulating layer is etched so as to expose thesurface of the metal layer, thereby providing holes passing through theinside of the metal hard mask and the interlayer insulating layer.

Furthermore, a method for producing the metal hard mask is notparticularly limited, and examples thereof include a method in which ametal layer including predetermined components is firstly formed on aninterlayer insulating layer, a resist film having a predeterminedpattern is formed thereon, and then the metal layer is etched using theresist film as a mask to produce a metal hard mask (that is, a film witha metal layer that is patterned).

In addition, the laminate may have layers other than the above-mentionedlayer, and examples of such other layers include an etching stop layerand an antireflection layer.

FIG. 1 illustrates a schematic cross-sectional view showing an exampleof a laminate which is an object to be cleaned in the method forcleaning a substrate of the embodiment of the present invention.

A laminate 10 shown in FIG. 1 comprises a metal layer 2, an etching stoplayer 3, an interlayer insulating layer 4, and a metal hard mask 5 inthis order on a substrate 1, and has holes 6 formed by a dry etchingstep, through which the metal layer 2 is exposed at predeterminedpositions. That is, the object to be cleaned shown in FIG. 1 is alaminate comprising the substrate 1, the metal layer 2, the etching stoplayer 3, the interlayer insulating layer 4, and the metal hard mask 5 inthis order, and comprising the holes 6 passing through the surface ofthe metal hard mask 5 at aperture positions thereof to the surfaces ofthe metal layer 2. The inner wall 11 of the hole 6 is formed of across-sectional wall 11 a consisting of the etching stop layer 3, theinterlayer insulating layer 4, and the metal hard mask 5, and a bottomwall 11 b consisting of the exposed metal layer 2, and dry etchingresidues 12 adhere thereto.

The method for cleaning a substrate of the embodiment of the presentinvention can be suitably used in cleaning intended to remove the dryetching residues 12. That is, while being excellent in removalperformance of the dry etching residue 12, it is also excellent in theanticorrosion property of the inner wall 11 (for example, the metallayer 2 and the like) of the object to be cleaned.

In addition, the method for cleaning a substrate of the embodiment ofthe present invention may also be carried out for the laminate which hasbeen subjected to a dry ashing step after the dry etching step.

Hereinafter, each layer constituent material of the above-mentionedlaminate will be described.

(Metal Hard Mask)

The metal hard mask preferably contains at least one component selectedfrom the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN,ZrOx, HfOx, and TaOx. Here, x and y are numbers represented by x=1 to 3and y=1 or 2, respectively.

Examples of the material of the metal hard mask include TiN, WO₂, andZrO₂.

(Interlayer Insulating Layer)

A material for the interlayer insulating layer is not particularlylimited, and examples thereof include those having a dielectric constantk of preferably 3.0 or less, and more preferably 2.6 or less.

Specific examples of the material for the interlayer insulating layerinclude organic polymers such as SiO₂, SiOC-based materials, and apolyimide.

(Etching Stop Layer)

A material for the etching stop layer is not particularly limited.Specific examples of the material for the etching stop layer includeSiN-, SiON-, and SiOCN-based materials, and metal oxides such as AlOx.

(Metal Layer)

The wiring material forming the metal layer contains at least tungsten(W) or cobalt (Co). Further, these metals may be alloys with othermetals.

The wiring material of the present invention may further contain a metalother than W and Co, a metal nitride, or an alloy. Specific examplesthereof include copper, titanium, titanium-tungsten, titanium nitride,tantalum, tantalum compounds, chromium, chromium oxide, and aluminum.

(Substrate)

Examples of the “substrate” as mentioned herein include a semiconductorsubstrate consisting of a single layer and a semiconductor substrateconsisting of multiple layers.

A material constituting the semiconductor substrate including a singlelayer is not particularly limited, and in general, the semiconductorsubstrate is preferably formed of silicon, silicon germanium, Group IIIto V compounds such as GaAs, and any combinations thereof.

In a case of the semiconductor substrate including multiple layers, itsconfiguration is not particularly limited, and the substrate may have,for example, exposed integrated circuit structures such as interconnectstructures (interconnect features) such as a metal wire and a dielectricmaterial on the semiconductor substrate such as silicon as describedabove. Examples of the metals and the alloys used in the interconnectstructures include, but are not limited to, aluminum, aluminum alloyedwith copper, copper, titanium, tantalum, cobalt, silicon, titaniumnitride, tantalum nitride, and tungsten. Further, there may be aninterlayer dielectric layer, a silicon oxide layer, a silicon nitridelayer, a silicon carbide layer, a carbon-doped silicon oxide layer, orthe like on the semiconductor substrate.

<Treatment Step>

Hereinafter, the treatment liquid preparing step A and the cleaning stepB will be described, respectively, in detail.

(Treatment Liquid Preparing Step A)

The treatment liquid preparing step A is a step of preparing thetreatment liquid. The respective components used in the present step areas described above.

The procedure in the present step is not particularly limited, andexamples thereof include a method in which a hydroxylamine compound, anorganic basic compound, an alcohol-based solvent, and any othercomponents are added, stirred, and mixed to prepare a treatment liquid.Further, in a case where the respective components are added, they maybe added at once or may be added in portions over a plurality of times.

In addition, as the respective components included in the treatmentliquid, components classified into a semiconductor grade or componentsclassified into a high-purity grade equivalent thereto are preferablyused, and components which have been subjected to removal of foreignmatters by filtering and/or reduction in ion components with an ionexchange resin or the like are preferably used. Further, it ispreferable that the raw material components are mixed, and thensubjected to removal of foreign matters by filtering and/or reduction inion components with an ion exchange resin or the like are used.

Moreover, in a case where a concentrate of the treatment liquid isprepared, the concentrate is diluted to obtain a diluted solution beforethe cleaning step B is performed, and then the cleaning step B isperformed using this diluted solution. In this case, the dilution ispreferably performed using a diluting liquid containing water.

(Cleaning Step B)

Examples of an object to be cleaned to be cleaned in the cleaning step Binclude the above-mentioned laminate, and examples thereof include thelaminate 10 having holes formed by carrying out a dry etching step asdescribed above (see FIG. 1). In addition, the dry etching residues 12adhere to the inside of the holes 6 in the laminate 10.

In addition, the laminate which has been subjected to a dry ashing stepafter the dry etching step may be referred to as an object to becleaned.

A method for bringing the treatment liquid into contact with the objectto be cleaned is not particularly limited, but examples thereof includea method in which an object to be cleaned is immersed in a treatmentliquid contained in a tank, a method in which a treatment liquid issprayed onto an object to be cleaned, a method in which a treatmentliquid is flowed onto an object to be cleaned, and any combinationsthereof. From the viewpoint of the residue removal performance, themethod in which an object to be cleaned is immersed in a treatmentliquid is preferable.

A temperature of the treatment liquid is preferably set to 90° C. orlower, more preferably 25° C. to 80° C., still more preferably 30° C. to75° C., and particularly preferably 40° C. to 70° C.

The cleaning time can be adjusted depending on the cleaning method usedand the temperature of the treatment liquid.

In a case where cleaning is performed in an immersion batch mode (abatch mode in which a plurality of sheets of object to be cleaned areimmersed in a treatment tank to perform a treatment), the cleaning timeis, for example, 60 minutes or less, preferably 1 to 60 minutes, morepreferably 3 to 20 minutes, and still more preferably 4 to 15 minutes.

In a case where sheet-type cleaning is performed, the cleaning time is,for example, 10 seconds to 5 minutes, preferably 15 seconds to 4minutes, more preferably 15 seconds to 3 minutes, and still morepreferably 20 seconds to 2 minutes.

Furthermore, in order to further enhance the cleaning capability of thetreatment liquid, a mechanical stirring method may be used.

Examples of the mechanical stirring method include a method in which atreatment liquid is circulated on an object to be cleaned, a method inwhich a treatment liquid is flowed through or sprayed on an object to becleaned, and a method in which a treatment liquid is stirred with anultrasonic or a megasonic.

(Rinsing Step B2)

The method for cleaning a substrate using the treatment liquid of theembodiment of the present invention may further have a step (hereinafterreferred to as a “rinsing step B2”) of cleaning the object to be cleanedby rinsing it with a solvent after the cleaning step B.

The rinsing step B2 is preferably a step which is performed subsequentlyafter the cleaning step B, and involves rinsing performed with a rinsingsolvent (rinsing liquid) over 5 seconds to 5 minutes. The rinsing stepB2 may be performed using the above-mentioned mechanical stirringmethod.

Examples of the rinsing solvent include, but are not limited to,deionized (DI) water, methanol, ethanol, isopropyl alcohol,N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyllactate, and propylene glycol monomethyl ether acetate. Alternatively,an aqueous rinsing liquid (diluted aqueous ammonium hydroxide or thelike) with a pH>8 may be used.

As the rinsing solvent, an aqueous ammonium hydroxide solution, DIwater, methanol, ethanol, or isopropyl alcohol is preferable, theaqueous ammonium hydroxide solution, DI water, or isopropyl alcohol ismore preferable, and the aqueous ammonium hydroxide solution or DI wateris still more preferable.

As a method for bringing the rinsing solvent into contact with theobject to be cleaned, the above-mentioned method in which the treatmentliquid is brought into contact with an object to be cleaned can beapplied in the same manner.

The temperature of the rinsing solvent in the rinsing step B2 ispreferably 16° C. to 27° C.

(Drying Step B3)

The method for cleaning a substrate using the treatment liquid of theembodiment of the present invention may have a drying step B3 for dryingan object to be cleaned after the rinsing step B2.

The drying method is not particularly limited. Examples of the dryingmethod include a spin drying method, a method of flowing a dry gas ontoan object to be cleaned, a method of heating a substrate by a heatingmeans such as a hot plate and an infrared lamp, a Marangoni dryingmethod, a Rotagoni drying method, an isopropyl alcohol (IPA) dryingmethod, or any combinations thereof.

The drying time depends on a specific method used, but in general, it ispreferably 30 seconds to several minutes.

The object to be cleaned in the method for cleaning a substrate usingthe treatment liquid of the embodiment of the present invention is notlimited to a laminate comprising at least a metal layer containing oneor more selected from the group consisting of W and Co, an interlayerinsulating layer, and a metal hard mask in this order on a substrate, asdescribed above. That is, for example, the method can also be used toremove photoresist etching residues of a laminate comprising at least ametal layer containing one or more selected from the group consisting ofW and Co, an interlayer insulating layer, and a photoresist film in thisorder on a substrate.

EXAMPLES

Hereinbelow, the present invention will be described in more detail withreference to Examples. The materials, the amounts used, the proportions,the treatment details, the treatment procedure, and the like shown inExamples below may be modified as appropriate as long as themodifications do not depart from the spirit of the present invention.Therefore, the scope of the present invention should not be construed asbeing limited to Examples shown below. In addition, “%” means “mass %”unless otherwise specified.

[Preparation of Treatment Liquid]

The treatment liquids shown in Table 1 were each prepared. In addition,the contents of the respective components used in each treatment liquid(all based on mass) are as described in the table.

Here, various components shown in Table 1 which are all classified intoa semiconductor grade or a high-purity grade equivalent thereto wereused.

Various components used in the treatment liquid are shown below.

<Hydroxylamine Compound>

HA: Hydroxylamine

HAS: Hydroxylamine sulfate

<Organic Basic Compound>

Amine 1: Tetrahydrofurfurylamine

Amine 2: N-(2-Aminoethyl)piperazine

Amine 3: 1,8-Diazabicyclo[5.4.0]undecene-7

Amine 4: 1,4-Diazabicyclo[2.2.2]octane

Amine 5: Diethylethylenetriamine

Amine 6: Triethylenetetramine

Amine 7: Tetraethylenepentamine

TMAH: Tetramethylammonium hydroxide

TBAH: Tetrabuthyllammonium hydroxide

BeTMAH: Benzyltrimethylammonium hydroxide

<Alcohol-Based Solvent>

Sol. 01: 3-Methoxy-3-methyl-1-butanol

Sol. 02: 1,3-Dihydroxypropane

Sol. 03: 1,4-Dihydroxybutane

Sol. 04: 2,5-Dihydroxy-2,5-dimethylhexane

Sol. 05: Furfuryl alcohol

Sol. 06: Glycerin

Sol. 07: 2,4-Dihydroxy-2-methylpentane

Sol. 08: 3-Methoxy-1-butanol

Sol. 09: 3-Methoxy-3-methylbutanol

Sol. 10: Ethylene glycol

Sol. 11: 1,2-Propanediol

Sol. 12: Ethylene glycol monoethyl ether

Sol. 13: Ethylene glycol monobutyl ether

Sol. 14: Diethylene glycol monomethyl ether

Sol. 15: Diethylene glycol monoethyl ether

Sol. 16: Dipropylene glycol monomethyl ether

Sol. 17: 1,2-Butanediol

Furthermore, among the components, Sol. 01, 08, 09, and 12 to 16 arealcohol-based solvents each having an alkoxy group.

<Surfactant>

Surf. 01: Dodecylbenzenesulfonic acid

Surf. 02: (Dodecylphenoxy)benzene-disulfonic acid

Surf. 03: Polyoxyethylene lauryl ether (manufactured by Kao Corporation,molecular weight of more than 250)

Surf. 04: Polyoxyethylene polyoxypropylene glycol (manufactured byTakemoto Oil & Fat Co., Ltd., molecular weight of more than 250)

Surf. 05: Cetyltrimethylammonium bromide

Surf. 06: Cetylpyridinium chloride

Surf. 07: Benzethonium chloride

Surf. 08: Chlorhexidine dihydrochloride

Surf. 09: Distearyl dimethyl ammonium chloride

Surf. 10: Benzalkonium chloride (manufactured by Kao Corporation)

Surf. 11: Dequalinium Chloride

Surf. 12: Dodecyltrimethylammonium chloride

Surf. 13: Octadecylamine hydrochloride

Surf. 14: 1-Dodecylpyridinium chloride

Surf. 15: Lauryl glucoside

Surf. 16: Octylphenol ethoxylate

Surf. 17: 2-Alkyl-n-carboxymethyl-n-hydroxyethyl imidazolium betaine(manufactured by Takemoto Oil & Fat Co., Ltd.)

Surf. 18: Lauramidopropyl betaine

Surf. 19: Cocamidopropyl betaine (manufactured by Kao Corporation)

Furthermore, among the components, Surf. 1 and 2 are anionicsurfactants.

Surf. 5 to 14 are cationic surfactants. Among those, the amine salt isSurf. 8 or 13. The pyridinium salt is Surf. 6, 11, or 14. The quaternaryammonium salt is 5, 7, 9, 10, or 12.

Surf. 3, 4, 15, and 16 are nonionic surfactants.

Surf. 17 to 19 are amphoteric surfactants.

<Tertiary Amine Compound and Alkyl Halide Compound>

Chem. 01: Trimethylamine

Chem. 02: 1-Chlorohexadecane

Chem. 03: Pyridine

Chem. 04:N,N-Dimethyl-2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethanamine

Chem. 05: Benzyl chloride

Chem. 06: Dimethyl stearyl amine

Chem. 07: 1-Chlorooctadecane

Chem. 08: 4-Amino-2-methylquinoline

Chem. 09: 1,10-Dichlorodecane

Chem. 10: 1-Chlorooctadecane

Chem. 11: 1-Chlorododecane

Furthermore, among the components, Chem. 01, 03, 04, 06, 08 are tertiaryamine compounds.

Chem. 02, 05, 07, 09, 10, and 11 are alkyl halide compounds.

<Acid>

O.A. 1: Citric acid

<Reducing Agent>

Red. 1: Thioglycollic acid

Red. 2: Gallic acid

Red. 3: Cathecol

Red. 4: α-Thioglycerol

Among the components, Red. 1 and 4 are mercaptan compounds, and Red. 2and 3 are catechol or catechol derivatives.

<Water>

Water: Ultrapure water

<pH Adjusting Agent>

As a pH adjusting agent, an inorganic acid (H₃PO₄) or an inorganic base(KOH) other than the treatment liquids of Examples 20 and 55 was addedso that the pH of the final treatment liquid would be a predeterminedvalue.

In addition, in a case where an inorganic base was used as the pHadjusting agent, the amount of the added inorganic base was 0.1% by massor less with respect to the total mass of the treatment liquid.

In Examples 20 and 55, an organic basic compound,1,8-diazabicyclo[5.4.0]undecene-7 (DBU (Amine 3)) was used as the pHadjusting agent. In other words, in Examples 20 and 55, the pH wasadjusted by adjusting the addition amount of the organic basic compound.

<Acetic Acid>

Acetic acid

<Preparation of Treatment Liquid (Metal-Containing Particles)>

The components were mixed so as to have the formulation and pH shown inTable 1 to obtain a mixed liquid. Next, the obtained mixed liquid wasfiltered with a filter to obtain a treatment liquid. In the filtration,the content of the metal-containing particles in the treatment liquidwas adjusted by adjusting the type of a filter used and/or the number oftimes of filtration.

In addition, the content of the metal-containing particles in thetreatment liquid was measured using Agilent 8900 triple quadrupoleSNP-ICP/MS (for semiconductor analysis, Option #200).

Furthermore, the definition of the metal-containing particles is asdescribed above.

[Evaluations]

Each of the treatment liquids prepared above was subjected to variousevaluations shown below.

<Etching Test>

Each of the treatment liquids of Examples and Comparative Examples wasprepared and then the W film or the Co film was subjected to an etchingtreatment.

Specifically, a substrate (substrate having a metal layer formedthereon) having a layer consisting of Co or a layer consisting of W by achemical vapor deposition (CVD) method formed on one surface of asubstrate (silicon wafer (diameter: 12 inches)) was prepared.

Furthermore, the substrate having the metal layer formed thereon wasimmersed in the treatment liquid (65° C.) of each of Examples andComparative Examples for 5 minutes, and an etching rate (Å/min) of thetreatment liquid for each metal layer was calculated from a differencein the thickness of the layer consisting of Co or the layer consistingof W between before and after the immersion in the treatment liquid. Thelower the etching rate for Co or W as measured in this test, the betterthe anticorrosion property for Co or W, respectively.

<Defect Suppression Property>

The substrate on which the layer formed of Co was formed was sprayed for1 minute at a flow rate of 1.0 L/min and 1.5 L/min, respectively, in theorder of the treatment liquid (65° C.) of each of Examples andComparative Examples, and water, and finally, a nitrogen gas was blownonto the substrate at a flow rate of 50 L/min.

Thereafter, the number of defects (pieces/cm²) in size (major axis) of60 nm or more as an object to be measured was counted using a surfacedefect inspection device (Surfscan SP-2, manufactured by KLA-TencorCorporation). From the obtained results, the defect suppression propertyof each treatment liquid was evaluated based on the following standard.

A: The number of defects is less than 0.5/cm².

B: The number of defects is 0.5/cm² or more and less than 1.0/cm².

C: The number of defects is 1.0/cm² or more and less than 2.0/cm².

D: The number of defects is 2.0/cm² or more and less than 3.0/cm².

E: The number of defects is 3.0/cm² or more.

<Residue Removal Property>

The residue removal performance was evaluated using each of thetreatment liquids of Examples and Comparative Examples. Further, in thefollowing evaluation, a model film formed of TiO₂, which is a kind ofresidue generated in a case where a metal hard mask (MHM) wasplasma-etched, was prepared, and by evaluating an etching rate thereof,the residue removal performance was evaluated. That is, it can be saidthat in a case where the etching rate is high, the residue removalperformance is excellent, whereas in a case where the etching rate islow, the residue removal performance is poor.

In addition, a model film (TiO₂ film) formed of TiO₂ is provided on anSi substrate with a film thickness of 1,000 Å.

Each of the treatment liquids of Examples and Comparative Examples wasprepared and then the TiO₂ film was subjected to an etching treatment.Specifically, the TiO₂ film was immersed in the treatment liquid (65°C.) of each of Examples and Comparative Examples for 5 minutes, andbased on a difference in the film thickness between before and after theimmersion in the treatment liquid, an etching rate (Å/min) wascalculated.

Furthermore, the thickness of the TiO₂ film before and after thetreatment was measured using an ellipsometer (spectroscopicellipsometer, trade name “Vase”, manufactured by J.A. Woollam Co., Inc.)under the conditions of a measurement range of 250 to 1,000 nm andmeasurement angles of 70 degrees and 75 degrees.

Based on the calculated etching rate (ER) of the TiO₂ film, the residueremoval property was evaluated according to the following evaluationstandard.

A: 1.5 Å/min<ER

B: 1.0 Å/min<ER≤1.5 Å/min

C: 0.5 Å/min<ER≤1.0 Å/min

D: 0.3 Å/min<ER≤0.5 Å/min

E: ER≤0.3 Å/min

The evaluation of the residue removal performance was carried out notonly for the treatment liquid immediately after preparation (“0 h” inthe tables) but also for the treatment liquid after being stored for 6hours at 65° C. under a sealed condition (“6 h” in the tables) and thetreatment liquid after being stored under the same condition for 12hours (“12 h” in the tables), the residue removal property of thetreatment liquids was evaluated.

Here, the etching rate of the TiO₂ film in a case of using the treatmentliquid immediately after preparation was taken as ER_(0h), and theetching rate in a case of using the treatment liquid after being storedfor 6 hours and the etching rate in a case of using the treatment liquidafter being stored for 12 hours were taken as ER_(6h) and ER_(12h),respectively. The maintenance rates of the etching rates at therespective storage times were calculated as “ER_(6h)/ER_(0h)” and“ER_(12h)/ER_(0h)”, respectively, and the temporal stability wasevaluated according to the following evaluation standard.

A: 0.90<Maintenance rate

B: 0.80<Maintenance rate≤0.90

C: 0.70<Maintenance rate≤0.80

D: 0.60<Maintenance rate≤0.70

E: Maintenance rate≤0.60

[Results]

The formulations of the respective treatment liquids and the testresults are shown in the following table.

In the tables, the “organic basic compound” is simply described as“Basic compound”.

%, ppm, ppb, and ppt shown as a content of each component in the columnof “Formulation” means % by mass, ppm by mass, ppb by mass, and ppt bymass, respectively.

The description of “Balance” indicated as the content of water meansthat as the finally obtained treatment liquid contains the components inthe amounts shown in the column of each component and the amount of thepH adjusting agent is adjusted so as to give a predetermined pH, theresidual component is water.

The description of “Inorganic acid/inorganic base” in the column of “pHAdjusting agent” indicates that an inorganic acid (H₃PO₄) or aninorganic base (KOH) as the pH adjusting agent is added in the amount sothat the pH of the treatment liquid is the one as described in thecolumn of “pH”. The description of “DBU 0.1%” in Examples 20 and 55indicates that 1,8-diazabicyclo[5.4.0]undecene-7 as the pH adjustingagent is added in the amount of 0.1% by mass with respect to the totalmass of the treatment liquid.

The column of “HA/Surfactant” means a mass ratio of the content of thehydroxylamine compound to the content of the surfactant in the treatmentliquid (Content of hydroxylamine compound/Content of surfactant).

The column of “Basic compound/surfactant” means a mass ratio of thecontent of the organic basic compound to the content of the surfactantin the treatment liquid (Content of organic basic compound/content ofsurfactant).

The column of “Co ER” and the column of “W ER” mean the etching ratesfor W and Co, respectively, of each treatment liquid.

TABLE 1 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-1 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 3.1 Balance 1 10.0% 1.0% 40% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 2 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01Chem. 02 0.7 Balance 3 10.0% 1.0% 70% 0.1% 10 ppt 10 ppt Example HA TMAHSol. 01 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 4 10.0% 1.0% 85.0% 0.1%10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.4Balance 5 0.5% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf.05 Chem. 01 Chem. 02 0.5 Balance 6 1.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.7 Balance 7 3.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01Chem. 02 0.7 Balance 8 5.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAHSol. 01 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 9 8.0% 1.0% 60% 0.1% 10ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.4Balance 10 12.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 1.8 Balance 11 15.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 2.4 Balance 1220.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem.01 Chem. 02 3.5 Balance 13 25.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.9 Balance 14 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 021.8 Balance 15 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 1.3 Balance 16 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.4 Balance 1710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem.01 Chem. 02 1.9 Balance 18 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 19 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co W Defectremoval Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-1 agent pH surfactantsurfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 16 15 C C D D 1 acid/inorganic base Example Inorganic 11 10010 4 4 B A B B 2 acid/inorganic base Example Inorganic 11 100 10 3 4 B BB B 3 acid/inorganic base Example Inorganic 11 100 10 3 5 D D B B 4acid/inorganic base Example Inorganic 11 5 10 1 3 D D B B 5acid/inorganic base Example Inorganic 11 10 10 2 3 C C B B 6acid/inorganic base Example Inorganic 11 30 10 3 4 C C B B 7acid/inorganic base Example Inorganic 11 50 10 3 4 C C B B 8acid/inorganic base Example Inorganic 11 80 10 3 5 B B B B 9acid/inorganic base Example Inorganic 11 120 10 6 8 B A B B 10acid/inorganic base Example Inorganic 11 150 10 8 10 B A B B 11acid/inorganic base Example Inorganic 11 200 10 12 12 B B B B 12acid/inorganic base Example Inorganic 11 250 10 15 20 B B B B 13acid/inorganic base Example Inorganic 8 100 10 16 3 D D B B 14acid/inorganic base Example Inorganic 9 100 10 14 4 C C B B 15acid/inorganic base Example Inorganic 10 100 10 8 5 C C B B 16acid/inorganic base Example Inorganic 12 100 10 4 10 B B B B 17acid/inorganic base Example Inorganic 13 100 10 3 16 B B B B 18acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 19acid/inorganic base

TABLE 2 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-2 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 1 Sol. 16 Surf. 05Chem. 01 Chem. 02 1.2 Balance 20 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 1 Sol. 16 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 2110.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 2 Sol. 16Surf. 05 Chem. 01 Chem. 02 0.9 Balance 22 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 2 Sol. 16 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 2310.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 3 Sol. 16Surf. 05 Chem. 01 Chem. 02 0.8 Balance 24 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 3 Sol. 16 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 2510.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 4 Sol. 16Surf. 05 Chem. 01 Chem. 02 1.0 Balance 26 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 4 Sol. 16 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 2710.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 5 Sol. 16Surf. 05 Chem. 01 Chem. 02 1.0 Balance 28 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 5 Sol. 16 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 2910.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 6 Sol. 16Surf. 05 Chem. 01 Chem. 02 0.8 Balance 30 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 6 Sol. 16 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 3110.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 7 Sol. 16Surf. 05 Chem. 01 Chem. 02 1.0 Balance 32 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Evaluation Formulation Residue pH Basic Co W Defect removal TemporalTemporal Table Adjusting HA/ compound/ ER ER suppression propertystability stability 1-2 agent pH surfactant surfactant (Å/min) (Å/min)property (0 h) (6 h) (12 h) Example DBU 0.1% 11 100 11 4 8 B A B B 20Example Inorganic 11 100 10 4 8 B A B B 21 acid/inorganic base ExampleInorganic 11 100 10 5 4 B A B B 22 acid/inorganic base Example Inorganic11 100 10 5 4 B A B B 23 acid/inorganic base Example Inorganic 11 100 103 5 B A B B 24 acid/inorganic base Example Inorganic 11 100 10 3 5 B A BB 25 acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 26acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 27acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 28acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 29acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 30acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 31acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 32acid/inorganic base

TABLE 3 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-3 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 16 Surf. 05Chem. 01 Chem. 02 1.0 Balance 33 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH0.5% Example HA TMAH Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1Balance 34 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.5 Balance 35 10.0% 1.0% 65% 5% 0.1%10 ppt 10 ppt Example HA TMAH Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 020.5 Balance 36 10.0% 1.0% 55% 15% 0.1% 10 ppt 10 ppt Example HA TMAHSol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.5 Balance 37 10.0% 1.0% 45%25% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Sol. 11 Surf. 05 Chem. 01Chem. 02 0.5 Balance 38 10.0% 1.0% 35% 35% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.5 Balance 39 10.0%1.0% 30% 40% 0.1% 10 ppt 10 ppt Example HA Amine 1 Sol. 01 Sol. 11 Surf05 Chem. 01 Chem. 02 0.9 Balance 40 10.0% 1.0% 60% 10% 0.1% 10 ppt 10ppt Example HA Amine 2 Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1Balance 41 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol.01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 42 10.0% 1.0% 60% 10%0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Sol. 11 Surf. 05 Chem. 01Chem. 02 1.1 Balance 43 10.0% 0.5% 60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5%Example HA Amine 4 Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1Balance 44 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol.01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 45 10.0% 1.0% 60% 10%0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 01 Sol. 11 Surf. 05 Chem. 01Chem. 02 1.1 Balance 46 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HAAmine 7 Sol. 01 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.3 Balance 47 10.0%1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 05 Surf. 05 Chem.01 Chem. 02 1.1 Balance 48 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 1 Sol. 05 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 49 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co W Defectremoval Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-3 agent pH surfactantsurfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 4 6 B A B B 33 acid/inorganic base Example Inorganic 11 100 104 7 B A B B 34 acid/inorganic base Example Inorganic 11 100 10 3 2 B A BB 35 acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 36acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 37acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 38acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 39acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 40acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 41acid/inorganic base Example Inorganic 11 100 10 3 8 B A B B 42acid/inorganic base Example Inorganic 11 100 10 3 8 B A B B 43acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 44acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 45acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 46acid/inorganic base Example Inorganic 11 100 10 5 8 B A B B 47acid/inorganic base Example Inorganic 11 100 10 3 8 B A B B 48acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 49acid/inorganic base

TABLE 4 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-4 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 2 Sol. 05 Surf. 05Chem. 01 Chem. 02 1.1 Balance 50 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 05 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 5110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 05 Surf. 05Chem. 01 Chem. 02 0.9 Balance 52 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH0.5% Example HA Amine 4 Sol. 05 Surf. 05 Chem. 01 Chem. 02 1.1 Balance53 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol. 05 Surf. 05Chem. 01 Chem. 02 0.8 Balance 54 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 6 Sol. 05 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 5510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 05 Surf. 05Chem. 01 Chem. 02 0.9 Balance 56 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 06 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 57 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 1 Sol. 06 Surf. 05 Chem. 01Chem. 02 1.3 Balance 58 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 2 Sol. 06 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 59 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 06 Surf. 05 Chem. 01 Chem. 021.0 Balance 60 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol.06 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 61 10.0% 0.5% 60% 0.1% 10 ppt10 ppt TMAH 0.5% Example HA Amine 4 Sol. 06 Surf. 05 Chem. 01 Chem. 021.1 Balance 62 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol.06 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 63 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA Amine 6 Sol. 06 Surf. 05 Chem. 01 Chem. 02 1.1 Balance64 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 06 Surf. 05Chem. 01 Chem. 02 0.8 Balance 65 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 07 Surf 05 Chem. 01 Chem. 02 1.1 Balance 66 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co WDefect removal Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-4 agent pH surfactantsurfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 4 7 B A B B 50 acid/inorganic base Example Inorganic 11 100 103 6 B A B B 51 acid/inorganic base Example Inorganic 11 100 10 3 6 B A BB 52 acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 53acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 54acid/inorganic base Example DBU 0.1% 11 100 11 4 7 B A B B 55 ExampleInorganic 11 100 10 3 6 B A B B 56 acid/inorganic base Example Inorganic11 100 10 4 7 B A B B 57 acid/inorganic base Example Inorganic 11 100 105 8 B A B B 58 acid/inorganic base Example Inorganic 11 100 10 3 8 B A BB 59 acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 60acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 61acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 62acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 63acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 64acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 65acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 66acid/inorganic base

TABLE 5 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-5 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 1 Sol. 07 Surf. 05Chem. 01 Chem. 02 1.1 Balance 67 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 2 Sol. 07 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 6810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 07 Surf. 05Chem. 01 Chem. 02 1.0 Balance 69 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 07 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 7010.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 4 Sol. 07Surf. 05 Chem. 01 Chem. 02 1.0 Balance 71 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 5 Sol. 07 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 7210.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 07 Surf. 05Chem. 01 Chem. 02 0.9 Balance 73 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 07 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 7410.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 10 Surf. 05 Chem.01 Chem. 02 0.8 Balance 75 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 1 Sol. 10 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 76 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 10 Surf. 05 Chem. 01 Chem. 021.1 Balance 77 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol.10 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 78 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA Amine 3 Sol. 10 Surf. 05 Chem. 01. Chem. 02 1.1Balance 79 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine4 Sol. 10 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 80 10.0% 1.0% 60% 0.1%10 ppt 10 ppt Example HA Amine 5 Sol. 10 Surf. 05 Chem. 01 Chem. 02 0.8Balance 81 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 10Surf. 05 Chem. 01 Chem. 02 0.8 Balance 82 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA Amine 7 Sol. 10 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 8310.0% 1.0% 60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pHBasic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-5 agent pHsurfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 5 6 B A B B 67 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 68 acid/inorganic base Example Inorganic11 100 10 4 6 B A B B 69 acid/inorganic base Example Inorganic 11 100 104 6 B A B B 70 acid/inorganic base Example Inorganic 11 100 10 4 6 B A BB 71 acid/inorganic base Example Inorganic 11 100 10 3 8 B A B B 72acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 73acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 74acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 75acid/inorganic base Example Inorganic 11 100 10 4 8 B A B B 76acid/inorganic base Example Inorganic 11 100 10 5 6 B A B B 77acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 78acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 79acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 80acid/inorganic base Example Inorganic 11 100 10 4 4 B A B B 81acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 82acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 83acid/inorganic base

TABLE 6 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-6 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 11 Surf. 05Chem. 01 Chem. 02 1.1 Balance 84 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 1 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 8510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 11 Surf. 05Chem. 01 Chem. 02 1.2 Balance 86 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 8710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 11 Surf. 05Chem. 01 Chem. 02 1.1 Balance 88 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH0.5% Example HA Amine 4 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance89 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol. 11 Surf. 05Chem. 01 Chem. 02 1.0 Balance 90 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 6 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 9110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 11 Surf. 05Chem. 01 Chem. 02 0.8 Balance 92 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 12 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 93 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 1 Sol. 12 Surf. 05 Chem. 01Chem. 02 0.8 Balance 94 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 2 Sol. 12 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 95 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 12 Surf. 05 Chem. 01 Chem. 020.8 Balance 96 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol.12 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 97 10.0% 0.5% 60% 0.1% 10 ppt10 ppt TMAH 0.5% Example HA Amine 4 Sol. 12 Surf. 05 Chem. 01 Chem. 021.0 Balance 98 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol.12 Surf. 05 Chem. 01 Chem. 02 1.3 Balance 99 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA Amine 6 Sol. 12 Surf. 05 Chem. 01 Chem. 02 0.8 Balance100 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pHBasic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-6 agent pHsurfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 4 7 B A B B 84 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 85 acid/inorganic base Example Inorganic11 100 10 4 8 B A B B 86 acid/inorganic base Example Inorganic 11 100 105 6 B A B B 87 acid/inorganic base Example Inorganic 11 100 10 5 6 B A BB 88 acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 89acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 90acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 91acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 92acid/inorganic base Example Inorganic 11 100 10 4 8 B A B B 93acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 94acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 95acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 96acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 97acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 98acid/inorganic base Example Inorganic 11 100 10 5 8 B A B B 99acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 100acid/inorganic base

TABLE 7 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-7 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 12 Surf. 05Chem. 01 Chem. 02 1.0 Balance 101 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 13 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 102 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 1 Sol. 13 Surf. 05 Chem. 01Chem. 02 0.8 Balance 103 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 2 Sol. 13 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 104 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 13 Surf. 05 Chem. 01Chem. 02 0.8 Balance 105 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 13 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 106 10.0% 0.5%60% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 4 Sol. 13 Surf. 05Chem, 01 Chem. 02 1.0 Balance 107 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 5 Sol. 13 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 10810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 13 Surf. 05Chem. 01 Chem. 02 1.1 Balance 109 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 13 Surf. 05 Chem. 01 Chem. 02 1.3 Balance 11010.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 14 Surf 05 Chem.01 Chem. 02 0.8 Balance 111 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 1 Sol. 14 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 112 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 14 Surf. 05 Chem. 01Chem. 02 1.1 Balance 113 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 14 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 114 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 14 Surf. 05 Chem. 01Chem. 02 0.9 Balance 115 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5%Example HA Amine 4 Sol. 14 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 11610.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol. 14 Surf. 05Chem. 01 Chem. 02 1.1 Balance 117 10.0% 1.0% 60% 0.1% 10 ppt 10 pptEvaluation Formulation Residue pH Basic Co W Defect removal TemporalTemporal Table Adjusting HA/ compound/ ER ER suppression propertystability stability 1-7 agent pH surfactant surfactant (Å/min) (Å/min)property (0 h) (6 h) (12 h) Example Inorganic 11 100 10 4 6 B A B B 101acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 102acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 103acid/inorganic base Example Inorganic 11 100 10 4 8 B A B B 104acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 105acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 106acid/inorganic base Example Inorganic 11 100 10 4 6 B A B B 107acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 108acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 109acid/inorganic base Example Inorganic 11 100 10 5 8 B A B B 110acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 111acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 112acid/inorganic base Example Inorganic 11 100 10 4 7 B A B B 113acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 114acid/inorganic base Example Inorganic 11 100 10 3 6 B A B B 115acid/inorganic base Example Inorganic 11 100 10 4 8 B A B B 116acid/inorganic base Example Inorganic 11 100 10 5 6 B A B B 117acid/inorganic base

TABLE 8 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-8 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 6 Sol. 14 Surf. 05Chem. 01 Chem. 02 0.8 Balance 118 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 14 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 11910.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 15 Surf. 05 Chem.01 Chem. 02 1.0 Balance 120 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 1 Sol. 15 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 121 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 15 Surf. 05 Chem. 01Chem. 02 1.1 Balance 122 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 15 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 123 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 15 Surf. 05 Chem. 01Chem. 02 0.8 Balance 124 10.0% 0.5% 60% 0.1% 10 ppt 10 ppt TMAH 0.5%Example HA Amine 4 Sol. 15 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 12510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 5 Sol. 15 Surf. 05Chem. 01 Chem. 02 0.8 Balance 126 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 6 Sol. 15 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 12710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Surf. 05Chem. 01 Chem. 02 1.3 Balance 128 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 1 Sol. 16 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 12910.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 16 Surf. 05Chem. 01 Chem. 02 1.0 Balance 130 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 5 Sol. 16 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 13110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 16 Surf. 05Chem. 01 Chem. 02 1.1 Balance 132 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 13310.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 14 Sol. 11 Surf.05 Chem. 01 Chem. 02 0.8 Balance 134 10.0% 1.0% 60% 10% 0.1% 10 ppt 10ppt Example HA Amine 1 Sol. 14 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.0Balance 135 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Evaluation FormulationResidue pH Basic Co W Defect removal Temporal Temporal Table AdjustingHA/ compound/ ER ER suppression property stability stability 1-8 agentpH surfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 3 5 B A B B 118 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 119 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 120 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 121 acid/inorganic base ExampleInorganic 11 100 10 4 7 B A B B 122 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 123 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 124 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 125 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 126 acid/inorganic base ExampleInorganic 11 100 10 4 8 B A B B 127 acid/inorganic base ExampleInorganic 11 100 10 5 8 B A B B 128 acid/inorganic base ExampleInorganic 11 100 10 4 7 B A B B 129 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 130 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 131 acid/inorganic base ExampleInorganic 11 100 10 4 7 B A B B 132 acid/inorganic base ExampleInorganic 11 100 10 5 6 B A B B 133 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 134 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 135 acid/inorganic base

TABLE 9 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-9 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 2 Sol. 14 Sol. 11Surf. 05 Chem. 01 Chem. 02 1.1 Balance 136 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 3 Sol. 14 Sol. 11 Surf. 05 Chem. 01 Chem. 020.8 Balance 137 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3Sol. 14 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 138 10.0% 0.5%60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 4 Sol. 14 Sol. 11Surf. 05 Chem. 01 Chem. 02 1.0 Balance 139 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 5 Sol. 14 Sol. 11 Surf. 05 Chem. 01 Chem. 020.8 Balance 140 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 6Sol. 14 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 141 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 14 Sol. 11 Surf. 05Chem. 01 Chem. 02 0.8 Balance 142 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 15 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.0 Balance143 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 1 Sol. 15Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.1 Balance 144 10.0% 1.0% 60% 10%0.1% 10 ppt 10 ppt Example HA Amine 2 Sol. 15 Sol. 11 Surf. 05 Chem. 01Chem. 02 0.8 Balance 145 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt ExampleHA Amine 3 Sol. 15 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 14610.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 15 Sol. 11Surf. 05 Chem. 01 Chem. 02 0.9 Balance 147 10.0% 0.5% 60% 10% 0.1% 10ppt 10 ppt TMAH 0.5% Example HA Amine 4 Sol. 15 Sol. 11 Surf. 05 Chem.01 Chem. 02 1.0 Balance 148 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 5 Sol. 15 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8Balance 149 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 6Sol. 15 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 150 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Sol. 11 Surf. 05Chem. 01 Chem. 02 1.1 Balance 151 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance152 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Evaluation Formulation ResiduepH Basic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-9 agent pHsurfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 4 7 B A B B 136 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 137 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 138 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 139 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 140 acid/inorganic base ExampleInorganic 11 100 10 4 7 B A B B 141 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 142 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 143 acid/inorganic base ExampleInorganic 11 100 10 5 6 B A B B 144 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 145 acid/inorganic base ExampleInorganic 11 100 10 4 5 B A B B 146 acid/inorganic base ExampleInorganic 11 100 10 4 5 B A B B 147 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 148 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 149 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 150 acid/inorganic base ExampleInorganic 11 100 10 4 7 B A B B 151 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 152 acid/inorganic base

TABLE 10 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-10 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 1 Sol. 16 Sol. 11Surf. 05 Chem. 01 Chem. 02 1.2 Balance 153 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 1 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 021.2 Balance 154 10.0% 0.5% 60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5% ExampleHA Amine 2 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 15510.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA . Amine 2 Sol. 16 Sol.11 Surf. 05 Chem. 01 Chem. 02 0.9 Balance 156 10.0% 0.5% 60% 10% 0.1% 10ppt 10 ppt TMAH 0.5% Example HA Amine 3 Sol. 16 Sol. 11 Surf. 05 Chem.01 Chem. 02 0.8 Balance 157 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8Balance 158 10.0% 0.5% 60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HAAmine 4 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 159 10.0%1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 4 Sol. 16 Sol. 11 Surf.05 Chem. 01 Chem. 02 1.0 Balance 160 10.0% 0.5% 60% 10% 0.1% 10 ppt 10ppt TMAH 0.5% Example HA Amine 5 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem.02 1.0 Balance 161 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HAAmine 5 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.0 Balance 162 10.0%0.5% 60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5% Example HA Amine 6 Sol. 16Sol. 11 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 163 10.0% 1.0% 60% 10%0.1% 10 ppt 10 ppt Example HA Amine 6 Sol. 16 Sol. 11 Surf. 05 Chem. 01Chem. 02 0.8 Balance 164 10.0% 0.5% 60% 10% 0.1% 10 ppt 10 ppt TMAH 0.5%Example HA Amine 7 Sol. 16 Sol. 11 Surf. 05 Chem. 01 Chem. 02 1.0Balance 165 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Evaluation FormulationResidue pH Basic Co W Defect removal Temporal Temporal Table AdjustingHA/ compound/ ER ER suppression property stability stability 1-10 agentpH surfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 4 8 B A B B 153 acid/inorganic base ExampleInorganic 11 100 10 4 8 B A B B 154 acid/inorganic base ExampleInorganic 11 100 10 5 4 B A B B 155 acid/inorganic base ExampleInorganic 11 100 10 5 4 B A B B 156 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 157 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 158 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 159 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 160 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 161 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 162 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 163 acid/inorganic base ExampleInorganic 11 100 10 3 5 B A B B 164 acid/inorganic base ExampleInorganic 11 100 10 4 6 B A B B 165 acid/inorganic base

TABLE 11 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-11 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 16 Sol. 11Surf. 05 Chem. 01 Chem. 02 1.0 Balance 166 10.0% 0.5% 60% 10% 0.1% 10ppt 10 ppt TMAH 0.5% Example HA TMAH Sol. 02 Surf. 05 Chem. 01 Chem. 020.9 Balance 167 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.03 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 168 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 04 Surf. 05 Chem. 01 Chem. 02 0.8 Balance169 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 08 Surf. 05Chem. 01 Chem. 02 0.9 Balance 170 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 09 Surf. 05 Chem. 01 Chem. 02 0.8 Balance 171 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 17 Surf. 05 Chem. 01Chem. 02 1.1 Balance 172 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 01 1.0 Balance 173 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 01 Surf. 02 2.1 Balance 174 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 01 Surf. 03 2.1 Balance 175 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 01 Surf. 04 1.8 Balance 176 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 01 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 177 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 07 Chem. 04 Chem. 050.5 Balance 178 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.01 Surf. 08 0.8 Balance 179 10.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01Surf. 09 Chem. 06 Chem. 07 0.8 Balance 180 10.0% 1.0% 60% 0.1% 10 ppt 10ppt Example HA TMAH Sol. 01 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 18110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 11 Chem.08 Chem. 09 0.6 Balance 182 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 12 Chem. 01 Chem. 10 0.8 Balance 183 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co W Defectremoval Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-11 agent pH surfactantsurfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 4 6 B A B B 166 acid/inorganic base Example Inorganic 11 10010 3 6 B A B B 167 acid/inorganic base Example Inorganic 11 100 10 4 8 BA B B 168 acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B169 acid/inorganic base Example Inorganic 11 100 10 4 5 B A B B 170acid/inorganic base Example Inorganic 11 100 10 3 5 B A B B 171acid/inorganic base Example Inorganic 11 100 10 5 6 B A B B 172acid/inorganic base Example Inorganic 11 100 10 4 6 C B B B 173acid/inorganic base Example Inorganic 11 100 10 9 12 C B B B 174acid/inorganic base Example Inorganic 11 100 10 12 9 C B B B 175acid/inorganic base Example Inorganic 11 100 10 10 8 C B B B 176acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 177acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 178acid/inorganic base Example Inorganic 11 100 10 5 3 B A B B 179acid/inorganic base Example Inorganic 11 100 10 5 3 B A B B 180acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 181acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 182acid/inorganic base Example Inorganic 11 100 10 5 3 B A B B 183acid/inorganic base

TABLE 12 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-12 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 01 Surf. 13Chem. 01 Chem. 07 0.6 Balance 184 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 185 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 15 0.5 Balance186 10.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01 Surf. 16 1.6 Balance 18710.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01 Surf. 17 1.9 Balance 18810.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01 Surf. 18 2.4 Balance 18910.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01 Surf. 19 1.6 Balance 19010.0% 1.0% 60% 0.1% Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 021.3 Balance 191 10.0% 1.0% 60% 0.01% 10 ppt 10 ppt Example HA TMAH Sol.01 Surf. 05 Chem. 01 Chem. 02 3.7 Balance 192 10.0% 1.0% 60% 0.0085% 10ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 2.6Balance 193 10.0% 1.0% 60% 0.0045% 10 ppt 10 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 1.2 Balance 194 1.0% 1.0% 60% 2% 10 ppt 10ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 1950.5% 1.0% 60% 1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01Chem. 02 1.2 Balance 196 10.0% 0.5% 60% 1% 10 ppt 10 ppt Example HA TMAHSol. 01 Surf. 05 Chem. 01 Chem. 02 1.4 Balance 197 10.0% 0.5% 60% 0.1%10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.2Balance 198 5.0% 0.5% 60% 0.1% 10 ppt 10 ppt HAS 5% Example HA TMAH Sol.01 Surf. 06 Chem. 03 Chem. 02 0.5 Balance 199 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 01 Surf. 07 Chem. 04 Chem. 05 0.6 Balance200 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 080.3 Balance 201 10.0% 1.0% 60% 0.1% Evaluation Formulation Residue pHBasic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-12 agent pHsurfactant surfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 4 2 B A B B 184 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 185 acid/inorganic base ExampleInorganic 11 100 10 3 2 C B B B 186 acid/inorganic base ExampleInorganic 11 100 10 10 6 C B B B 187 acid/inorganic base ExampleInorganic 11 100 10 12 7 C B B B 188 acid/inorganic base ExampleInorganic 11 100 10 15 9 C B B B 189 acid/inorganic base ExampleInorganic 11 100 10 10 6 C B B B 190 acid/inorganic base ExampleInorganic 11 1,000 100 8 5 B A B B 191 acid/inorganic base ExampleInorganic 11 1,176 118 16 21 D C B B 192 acid/inorganic base ExampleInorganic 11 2,222 222 21 5 D C D D 193 acid/inorganic base ExampleInorganic 11 0.5 0.5 8 4 D D C D 194 acid/inorganic base ExampleInorganic 11 0.5 1 8 4 C D C C 195 acid/inorganic base Example Inorganic11 10 0.5 8 4 D C C D 196 acid/inorganic base Example Inorganic 11 100 58 4 C B B D 197 acid/inorganic base Example Inorganic 11 100 5 8 4 C B BD 198 acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 199acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 200acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 201acid/inorganic base

TABLE 13 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-13 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 01 Surf. 09Chem. 06 Chem. 07 0.5 Balance 202 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 203 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Surf. 12 Chem. 01Chem. 10 0.5 Balance 204 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.2 Balance 205 10.0% 1.0% 60%0.05% 10 ppt 20 ppt Surf. 06 Chem. 03 0.05% 10 ppt Example HA TMAH Sol.01 Surf. 05 Chem. 01 Chem. 02 0.5 Balance 206 10.0% 1.0% 60% 0.05% 10ppt 10 ppt Surf. 07 Chem. 04 Chem. 05 0.05% 10 ppt 10 ppt Example HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.6 Balance 207 10.0% 1.0% 60%0.05% 10 ppt 10 ppt Surf. 08 0.05% Example HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 0.3 Balance 208 10.0% 1.0% 60% 0.05% 10 ppt 10 pptSurf. 09 Chem. 06 Chem. 07 0.05% 10 ppt 10 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 0.5 Balance 209 10.0% 1.0% 60% 0.05% 20 ppt10 ppt Surf. 10 Chem. 05 0.05% 10 ppt Example HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 0.5 Balance 210 10.0% 1.0% 60% 0.05% 10 ppt 10 pptSurf. 11 Chem. 08 Chem. 09 0.05% 10 ppt 10 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 0.5 Balance 211 10.0% 1.0% 60% 0.05% 20 ppt10 ppt Surf. 12 Chem. 10 0.05% 10 ppt Example HA TBAH Sol. 01 Surf. 06Chem. 03 Chem. 02 0.5 Balance 212 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TBAH Sol. 01 Surf. 07 Chem. 04 Chem. 05 0.6 Balance 213 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co WDefect removal Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-13 agent pH surfactantsurfactant (Å/min) (Å/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 3 2 B A B B 202 acid/inorganic base Example Inorganic 11 10010 3 2 B A B B 203 acid/inorganic base Example Inorganic 11 100 10 3 2 BA B B 204 acid/inorganic base Example Inorganic 11 100 5 8 4 B A B B 205acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 206acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 207acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 208acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 209acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 210acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 211acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 212acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 213acid/inorganic base

TABLE 14 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-14 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TBAH Sol. 01 Surf. 08 0.3Balance 214 10.0% 1.0% 60% 0.1% Example HA TBAH Sol. 01 Surf. 09 Chem.06 Chem. 07 0.5 Balance 215 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATBAH Sol. 01 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 216 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TBAH Sol. 01 Surf. 11 Chem. 08 Chem. 050.5 Balance 217 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TBAH Sol.01 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 218 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TBAH Sol. 01 Surf. 13 Chem. 01 Chem. 07 0.6 Balance219 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TBAH Sol. 01 Surf. 14Chem. 03 Chem. 11 0.5 Balance 220 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA BeTMAH Sol. 01 Surf. 06 Chem. 03 Chem. 02 0.5 Balance 22110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA BeTMAH Sol. 01 Surf. 07Chem. 04 Chem. 05 0.6 Balance 222 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA BeTMAH Sol. 01 Surf. 08 0.3 Balance 223 10.0% 1.0% 60% 0.1%Example HA BeTMAH Sol. 01 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 22410.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA BeTMAH Sol. 01 Surf. 10Chem. 01 Chem. 05 0.5 Balance 225 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA BeTMAH Sol. 01 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 22610.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA BeTMAH Sol. 01 Surf. 12Chem. 01 Chem. 10 0.5 Balance 227 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA BeTMAH Sol. 01 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 22810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA BeTMAH Sol. 01 Surf. 14Chem. 03 Chem. 11 0.5 Balance 229 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 01 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 23010.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Surf. 07Chem. 04 Chem. 05 0.3 Balance 231 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 01 Surf. 08 0.3 Balance 232 10.0% 1.0% 60% 0.1%Evaluation Formulation Residue pH Basic Co W Defect removal TemporalTemporal Table Adjusting HA/ compound/ ER ER suppression propertystability stability 1-14 agent pH surfactant surfactant (Å/min) (Å/min)property (0 h) (6 h) (12 h) Example Inorganic 11 100 10 2 1 B A B B 214acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 215acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 216acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 217acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 218acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 219acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 220acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 221acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 222acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 223acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 224acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 225acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 226acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 227acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 228acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 229acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 230acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 231acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 232acid/inorganic base

TABLE 15 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-15 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 3 Sol. 01 Surf. 09Chem. 06 Chem. 07 0.5 Balance 233 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 01 Surf. 10 Chem. 01 Chem. 05 0.6 Balance 23410.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Surf. 11Chem. 08 Chem. 09 0.3 Balance 235 10.0% 1.0% 60% 0.1% 10 pp 10 pptExample HA Amine 3 Sol. 01 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 23610.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Surf. 13Chem. 01 Chem. 07 0.5 Balance 237 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 01 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 23810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Surf. 06Chem. 03 Chem. 02 0.5 Balance 239 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 01 Surf. 07 Chem. 04 Chem. 05 0.6 Balance 24010.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Surf. 080.5 Balance 241 10.0% 1.0% 60% 0.1% Example HA Amine 7 Sol. 01 Surf. 09Chem. 06 Chem. 07 0.6 Balance 242 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 01 Surf. 10 Chem. 01 Chem. 05 0.3 Balance 24310.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Surf. 11Chem. 08 Chem. 09 0.5 Balance 244 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 01 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 24510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Surf. 13Chem. 01 Chem. 07 0.6 Balance 246 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 01 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 24710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Sol. 11 Surf.06 Chem. 03 Chem. 02 0.6 Balance 248 10.0% 1.0% 60% 10% 0.1% 10 ppt 10ppt Example HA TMAH Sol. 01 Sol. 11 Surf. 07 Chem. 04 Chem. 05 0.3Balance 249 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.01 Sol. 11 Surf. 08 0.3 Balance 250 10.0% 1.0% 60% 10% 0.1% Example HATMAH Sol. 01 Sol. 11 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 251 10.0%1.0% 60% 10% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH BasicCo W Defect removal Temporal Temporal Table Adjusting HA/ compound/ ERER suppression property stability stability 1-15 agent pH surfactantsurfactant (A/min) (A/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 3 2 B A B B 233 acid/inorganic base Example Inorganic 11 10010 4 2 B A B B 234 acid/inorganic base Example Inorganic 11 100 10 2 1 BA B B 235 acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B236 acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 237acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 238acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 239acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 240acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 241acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 242acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 243acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 244acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 245acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 246acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 247acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 248acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 249acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 250acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 251acid/inorganic base

TABLE 16 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-16 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 01 Sol. 11Surf. 10 Chem. 01 Chem. 05 0.6 Balance 252 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA TMAH Sol. 01 Sol. 11 Surf. 11 Chem. 08 Chem. 090.3 Balance 253 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAHSol. 01 Sol. 11 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 254 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 01 Sol. 11 Surf. 13Chem. 01 Chem. 07 0.5 Balance 255 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Sol. 11 Surf. 14 Chem. 03 Chem. 11 0.5 Balance256 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01Sol. 11 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 257 10.0% 1.0% 60% 10%0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Sol. 11 Surf. 07 Chem. 04Chem. 05 0.5 Balance 258 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt ExampleHA Amine 3 Sol. 01 Sol. 11 Surf. 08 0.6 Balance 259 10.0% 1.0% 60% 10%0.1% Example HA Amine 3 Sol. 01 Sol. 11 Surf. 09 Chem. 06 Chem. 07 0.3Balance 260 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3Sol. 01 Sol. 11 Surf. 10 Chem. 01 Chem. 05 0.3 Balance 261 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Sol. 11 Surf. 11Chem. 08 Chem. 09 0.5 Balance 262 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 01 Sol. 11 Surf. 12 Chem. 01 Chem. 10 0.6Balance 263 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3Sol. 01 Sol. 11 Surf. 13 Chem. 01 Chem. 07 0.3 Balance 264 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 01 Sol. 11 Surf. 14Chem. 03 Chem. 11 0.5 Balance 265 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 01 Sol. 11 Surf. 06 Chem. 03 Chem. 02 0.5Balance 266 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7Sol. 01 Sol. 11 Surf. 07 Chem. 04 Chem. 05 0.5 Balance 267 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Sol. 11 Surf. 080.5 Balance 268 10.0% 1.0% 60% 10% 0.1% Example HA Amine 7 Sol. 01 Sol.11 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 269 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 7 Sol. 01 Sol. 11 Surf. 10 Chem. 01 Chem. 050.5 Balance 270 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt EvaluationFormulation Residue pH Basic Co W Defect removal Temporal Temporal TableAdjusting HA/ compound/ ER ER suppression property stability stability1-16 agent pH surfactant surfactant (A/min) (A/min) property (0 h) (6 h)(12 h) Example Inorganic 11 100 10 4 2 B A B B 252 acid/inorganic baseExample Inorganic 11 100 10 2 1 B A B B 253 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 254 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 255 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 256 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 257 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 258 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 259 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 260 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 261 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 262 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 263 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 264 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 265 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 266 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 267 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 268 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 269 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 270 acid/inorganic base

TABLE 17 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-17 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 01 Sol. 11Surf. 11 Chem. 08 Chem. 09 0.6 Balance 271 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 7 Sol. 01 Sol. 11 Surf. 12 Chem. 01 Chem. 100.5 Balance 272 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7Sol. 01 Sol. 11 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 273 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 01 Sol. 11 Surf. 14Chem. 03 Chem. 11 0.3 Balance 274 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 05 Surf. 06 Chem. 03 Chem. 02 0.3 Balance 275 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 05 Surf. 07 Chem. 04Chem. 05 0.5 Balance 276 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 05 Surf. 08 0.6 Balance 277 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 05 Surf. 09 Chem. 06 Chem. 07 0.3 Balance 278 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 05 Surf. 10 Chem. 01 Chem. 050.5 Balance 279 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.05 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 280 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 05 Surf. 12 Chem. 01 Chem. 10 0.5 Balance281 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 05 Surf. 13Chem. 01 Chem. 07 0.5 Balance 282 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 05 Surf. 14 Chem. 03 Chem. 11 0.6 Balance 283 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 05 Surf. 06 Chem. 03Chem. 02 0.3 Balance 284 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 05 Surf. 07 Chem. 04 Chem. 05 0.5 Balance 285 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 05 Surf. 08 0.6 Balance286 10.0% 1.0% 60% 0.1% Example HA Amine 3 Sol. 05 Surf. 09 Chem. 06Chem. 07 0.3 Balance 287 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 05 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 288 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 05 Surf. 11 Chem. 08Chem. 09 0.5 Balance 289 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt EvaluationFormulation Residue pH Basic Co W Defect removal Temporal Temporal TableAdjusting HA/ compound/ ER ER suppression property stability stability1-17 agent pH surfactant surfactant (A/min) (A/min) property (0 h) (6 h)(12 h) Example Inorganic 11 100 10 4 2 B A B B 271 acid/inorganic baseExample Inorganic 11 100 10 3 2 B A B B 272 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 273 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 274 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 275 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 276 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 277 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 278 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 279 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 280 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 281 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 282 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 283 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 284 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 285 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 286 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 287 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 288 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 289 acid/inorganic base

TABLE 18 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-18 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 3 Sol. 05 Surf. 12Chem. 01 Chem. 10 0.5 Balance 290 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 05 Surf. 13 Chem. 01 Chem. 07 0.5 Balance 29110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 05 Surf. 14Chem. 03 Chem. 11 0.5 Balance 292 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 05 Surf. 06 Chem. 03 Chem. 02 0.5 Balance 29310.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 05 Surf. 07Chem. 04 Chem. 05 0.6 Balance 294 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 05 Surf. 08 0.5 Balance 295 10.0% 1.0% 60% 0.1%Example HA Amine 7 Sol. 05 Surf. 09 Chem. 06 Chem. 07 0.6 Balance 29610.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 05 Surf. 10Chem. 01 Chem. 05 0.3 Balance 297 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 05 Surf. 11 Chem. 08 Chem. 09 0.3 Balance 29810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 05 Surf. 12Chem. 01 Chem. 10 0.5 Balance 299 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 05 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 30010.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 05 Surf. 14Chem. 03 Chem. 11 0.3 Balance 301 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 10 Surf. 06 Chem. 03 Chem. 02 0.3 Balance 302 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 10 Surf. 07 Chem. 04Chem. 05 0.5 Balance 303 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 10 Surf. 08 0.5 Balance 304 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 10 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 305 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 10 Surf. 10 Chem. 01 Chem. 050.5 Balance 306 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.10 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 307 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 10 Surf. 12 Chem. 01 Chem. 10 0.5 Balance308 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pHBasic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-18 agent pHsurfactant surfactant (A/min) (A/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 3 2 B A B B 290 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 291 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 292 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 293 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 294 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 295 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 296 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 297 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 298 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 299 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 300 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 301 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 302 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 303 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 304 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 305 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 306 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 307 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 308 acid/inorganic base

TABLE 19 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-19 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 10 Surf. 13Chem. 01 Chem. 07 0.6 Balance 309 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 10 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 310 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 10 Surf. 06 Chem. 03Chem. 02 0.6 Balance 311 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 10 Surf. 07 Chem. 04 Chem. 05 0.3 Balance 312 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 10 Surf. 08 0.3 Balance313 10.0% 1.0% 60% 0.1% Example HA Amine 3 Sol. 10 Surf. 09 Chem. 06Chem. 07 0.5 Balance 314 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 10 Surf. 10 Chem. 01 Chem. 05 0.3 Balance 315 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 10 Surf. 11 Chem. 08Chem. 09 0.3 Balance 316 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 10 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 317 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 10 Surf. 13 Chem. 01Chem. 07 0.6 Balance 318 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 10 Surf. 14 Chem. 03 Chem. 11 0.3 Balance 319 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 10 Surf. 06 Chem. 03Chem. 02 0.3 Balance 320 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 7 Sol. 10 Surf. 07 Chem. 04 Chem. 05 0.5 Balance 321 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 10 Surf. 08 0.5 Balance322 10.0% 1.0% 60% 0.1% Example HA Amine 7 Sol. 10 Surf. 09 Chem. 06Chem. 07 0.5 Balance 323 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 7 Sol. 10 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 324 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 10 Surf. 11 Chem. 08Chem. 09 0.5 Balance 325 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 7 Sol. 10 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 326 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 10 Surf. 13 Chem. 01Chem. 07 0.6 Balance 327 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt EvaluationFormulation Residue pH Basic Co W Defect removal Temporal Temporal TableAdjusting HA/ compound/ ER ER suppression property stability stability1-19 agent pH surfactant surfactant (A/min) (A/min) property (0 h) (6 h)(12 h) Example Inorganic 11 100 10 4 2 B A B B 309 acid/inorganic baseExample Inorganic 11 100 10 3 2 B A B B 310 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 311 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 312 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 313 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 314 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 315 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 316 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 317 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 318 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 319 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 320 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 321 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 322 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 323 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 324 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 325 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 326 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 327 acid/inorganic base

TABLE 20 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-20 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 10 Surf. 14Chem. 03 Chem. 11 0.5 Balance 328 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 14 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 329 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 14 Surf. 07 Chem. 04Chem. 05 0.3 Balance 330 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 14 Surf. 08 0.3 Balance 331 10.0% 1.0% 60% 0.1% Example HATMAH Sol. 14 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 332 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 14 Surf. 10 Chem. 01 Chem. 050.6 Balance 333 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.14 Surf. 11 Chem. 08 Chem. 09 0.3 Balance 334 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 14 Surf. 12 Chem. 01 Chem. 10 0.3 Balance335 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 14 Surf. 13Chem. 01 Chem. 07 0.3 Balance 336 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 14 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 337 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 14 Surf. 06 Chem. 03Chem. 02 0.6 Balance 338 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 14 Surf. 07 Chem. 04 Chem. 05 0.3 Balance 339 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 14 Surf. 08 0.3 Balance340 10.0% 1.0% 60% 0.1% Example HA Amine 3 Sol. 14 Surf. 09 Chem. 06Chem. 07 0.5 Balance 341 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 14 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 342 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 14 Surf. 11 Chem. 08Chem. 09 0.5 Balance 343 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 14 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 344 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 14 Surf. 13 Chem. 01Chem. 07 0.5 Balance 345 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 14 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 346 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co WDefect removal Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-20 agent pH surfactantsurfactant (A/min) (A/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 3 2 B A B B 328 acid/inorganic base Example Inorganic 11 10010 4 2 B A B B 329 acid/inorganic base Example Inorganic 11 100 10 2 1 BA B B 330 acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B331 acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 332acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 333acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 334acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 335acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 336acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 337acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 338acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 339acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 340acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 341acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 342acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 343acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 344acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 345acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 346acid/inorganic base

TABLE 21 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-21 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 14 Surf. 06Chem. 03 Chem. 02 0.6 Balance 347 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 14 Surf. 07 Chem. 04 Chem. 05 0.5 Balance 34810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 14 Surf. 080.6 Balance 349 10.0% 1.0% 60% 0.1% Example HA Amine 7 Sol. 14 Surf. 09Chem. 06 Chem. 07 0.3 Balance 350 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 14 Surf. 10 Chem. 01 Chem. 05 0.3 Balance 35110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 14 Surf. 11Chem. 08 Chem. 09 0.5 Balance 352 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 14 Surf. 12 Chem. 01 Chem. 10 0.6 Balance 35310.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 14 Surf. 13Chem. 01 Chem. 07 0.3 Balance 354 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 14 Surf. 14 Chem. 03 Chem, 11 0.5 Balance 35510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 15 Surf. 06 Chem.03 Chem. 02 0.6 Balance 356 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 15 Surf. 07 Chem. 04 Chem. 05 0.3 Balance 357 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 15 Surf. 08 0.3 Balance 35810.0% 1.0% 60% 0.1% Example HA TMAH Sol. 15 Surf. 09 Chem. 06 Chem. 070.5 Balance 359 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.15 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 360 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 15 Surf. 11 Chem. 08 Chem. 09 0.5 Balance361 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 15 Surf. 12Chem. 01 Chem. 10 0.5 Balance 362 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 15 Surf. 13 Chem. 01 Chem. 07 0.5 Balance 363 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 15 Surf. 14 Chem. 03Chem. 11 0.5 Balance 364 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HAAmine 3 Sol. 15 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 365 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pH Basic Co WDefect removal Temporal Temporal Table Adjusting HA/ compound/ ER ERsuppression property stability stability 1-21 agent pH surfactantsurfactant (A/min) (A/min) property (0 h) (6 h) (12 h) Example Inorganic11 100 10 4 2 B A B B 347 acid/inorganic base Example Inorganic 11 10010 3 2 B A B B 348 acid/inorganic base Example Inorganic 11 100 10 4 2 BA B B 349 acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B350 acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 351acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 352acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 353acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 354acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 355acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 356acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 357acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 358acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 359acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 360acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 361acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 362acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 363acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 364acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 365acid/inorganic base

TABLE 22 Formulation Metal- Alcohol - Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-22 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 3 Sol. 15 Surf. 07Chem. 04 Chem. 05 0.5 Balance 366 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 15 Surf. 08 0.6 Balance 367 10.0% 1.0% 60% 0.1%Example HA Amine 3 Sol. 15 Surf. 09 Chem. 06 Chem. 07 0.3 Balance 36810.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 15 Surf. 10Chem. 01 Chem. 05 0.3 Balance 369 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 15 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 37010.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 15 Surf. 12Chem. 01 Chem. 10 0.6 Balance 371 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 15 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 37210.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 15 Surf. 14Chem. 03 Chem. 11 0.3 Balance 373 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 15 Surf. 06 Chem. 03 Chem. 02 0.3 Balance 37410.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Surf. 07Chem. 04 Chem. 05 0.5 Balance 375 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 15 Surf. 08 0.5 Balance 376 10.0% 1.0% 60% 0.1%Example HA Amine 7 Sol. 15 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 37710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Surf. 10Chem. 01 Chem. 05 0.5 Balance 378 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 15 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 37910.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Surf. 12Chem. 01 Chem. 10 0.5 Balance 380 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 15 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 38110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 15 Surf. 14Chem. 03 Chem. 11 0.5 Balance 382 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 16 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 383 10.0%1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Surf. 07 Chem. 04Chem. 05 0.3 Balance 384 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt EvaluationFormulation Residue pH Basic Co W Defect removal Temporal Temporal TableAdjusting HA/ compound/ ER ER suppression property stability stability1-22 agent pH surfactant surfactant (A/min (A/min) property (0 h) (6 h)(12 h) Example Inorganic 11 100 10 3 2 B A B B 366 acid/inorganic baseExample Inorganic 11 100 10 4 2 B A B B 367 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 368 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 369 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 370 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 371 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 372 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 373 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 374 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 375 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 376 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 377 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 378 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 379 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 380 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 381 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 382 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 383 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 384 acid/inorganic base

TABLE 23 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-23 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 16 Surf. 08 0.3Balance 385 10.0% 1.0% 60% 0.1% Example HA TMAH Sol. 16 Surf. 09 Chem.06 Chem. 07 0.5 Balance 386 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HATMAH Sol. 16 Surf. 10 Chem. 01 Chem. 05 0.6 Balance 387 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Surf. 11 Chem. 08 Chem. 090.3 Balance 388 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.16 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 389 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 16 Surf. 13 Chem. 01 Chem. 07 0.6 Balance390 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Surf. 14Chem. 03 Chem. 11 0.3 Balance 391 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Surf. 06 Chem. 03 Chem. 02 0.3 Balance 39210.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Surf. 07Chem. 04 Chem. 05 0.5 Balance 393 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Surf. 08 0.5 Balance 394 10.0% 1.0% 60% 0.1%Example HA Amine 3 Sol. 16 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 39510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Surf. 10Chem. 01 Chem. 05 0.5 Balance 396 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Surf. 11 Chem. 08 Chem. 09 0.5 Balance 39710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Surf. 12Chem. 01 Chem. 10 0.5 Balance 398 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Surf. 13 Chem. 01 Chem. 07 0.6 Balance 39910.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Surf. 14Chem. 03 Chem. 11 0.5 Balance 400 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 06 Chem. 03 Chem. 02 0.6 Balance 40110.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Surf. 07Chem. 04 Chem. 05 0.3 Balance 402 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 08 0.3 Balance 403 10.0% 1.0% 60% 0.1%Evaluation Formulation Residue pH Basic Co W Defect removal TemporalTemporal Table Adjusting HA/ compound/ ER ER suppression propertystability stability 1-23 agent pH surfactant surfactant (A/min) (A/min)property (0 h) (6 h) (12 h) Example Inorganic 11 100 10 2 1 B A B B 385acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 386acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 387acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 388acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 389acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 390acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 391acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 392acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 393acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 394acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 395acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 396acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 397acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 398acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 399acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 400acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 401acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 402acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 403acid/inorganic base

TABLE 24 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-24 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 7 Sol. 16 Surf. 09Chem. 06 Chem. 07 0.5 Balance 404 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 10 Chem. 01 Chem. 05 0.6 Balance 40510.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Surf. 11Chem. 08 Chem. 09 0.6 Balance 406 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 12 Chem. 01 Chem. 10 0.3 Balance 40710.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Surf. 13Chem. 01 Chem. 07 0.3 Balance 408 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Surf. 14 Chem. 03 Chem. 11 0.5 Balance 40910.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Sol. 11 Surf.06 Chem. 03 Chem. 02 0.5 Balance 410 10.0% 1.0% 60% 10% 0.1% 10 ppt 10ppt Example HA TMAH Sol. 16 Sol. 11 Surf. 07 Chem. 04 Chem. 05 0.5Balance 411 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol.16 Sol. 11 Surf. 08 0.5 Balance 412 10.0% 1.0% 60% 10% 0.1% Example HATMAH Sol. 16 Sol. 11 Surf. 09 Chem. 06 Chem. 07 0.5 Balance 413 10.0%1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Sol. 11 Surf. 10Chem. 01 Chem. 05 0.5 Balance 414 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 16 Sol. 11 Surf. 11 Chem. 08 Chem. 09 0.6 Balance415 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAH Sol. 16 Sol.11 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 416 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA TMAH Sol. 16 Sol. 11 Surf. 13 Chem. 01 Chem. 070.6 Balance 417 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA TMAHSol. 16 Sol. 11 Surf. 14 Chem. 03 Chem. 11 0.3 Balance 418 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Sol. 11 Surf. 06Chem. 03 Chem. 02 0.3 Balance 419 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Sol. 11 Surf. 07 Chem. 04 Chem. 05 0.5Balance 420 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3Sol. 16 Sol. 11 Surf. 08 0.6 Balance 421 10.0% 1.0% 60% 10% 0.1% ExampleHA Amine 3 Sol. 16 Sol. 11 Surf. 09 Chem. 06 Chem. 07 0.6 Balance 42210.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Evaluation Formulation Residue pHBasic Co W Defect removal Temporal Temporal Table Adjusting HA/compound/ ER ER suppression property stability stability 1-24 agent pHsurfactant surfactant (A/min) (A/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 3 2 B A B B 404 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 405 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 406 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 407 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 408 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 409 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 410 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 411 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 412 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 413 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 414 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 415 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 416 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 417 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 418 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 419 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 420 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 421 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 422 acid/inorganic base

TABLE 25 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-25 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA Amine 3 Sol. 16 Sol. 11Surf. 10 Chem. 01 Chem. 05 0.3 Balance 423 10.0% 1.0% 60% 10% 0.1% 10ppt 10 ppt Example HA Amine 3 Sol. 16 Sol. 11 Surf. 11 Chem. 08 Chem. 090.3 Balance 424 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3Sol. 16 Sol. 11 Surf. 12 Chem. 01 Chem. 10 0.5 Balance 425 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 3 Sol. 16 Sol. 11 Surf. 13Chem. 01 Chem. 07 0.5 Balance 426 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 3 Sol. 16 Sol. 11 Surf. 14 Chem. 03 Chem. 11 0.5Balance 427 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7Sol. 16 Sol. 11 Surf. 06 Chem. 03 Chem. 02 0.5 Balance 428 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Sol. 11 Surf. 07Chem. 04 Chem. 05 0.5 Balance 429 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA Amine 7 Sol. 16 Sol. 11 Surf. 08 0.5 Balance 430 10.0% 1.0%60% 10% 0.1% Example HA Amine 7 Sol. 16 Sol. 11 Surf. 09 Chem. 06 Chem.07 0.6 Balance 431 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HAAmine 7 Sol. 16 Sol. 11 Surf. 10 Chem. 01 Chem. 05 0.5 Balance 432 10.0%1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Sol. 11 Surf.11 Chem. 08 Chem. 09 0.6 Balance 433 10.0% 1.0% 60% 10% 0.1% 10 ppt 10ppt Example HA Amine 7 Sol. 16 Sol. 11 Surf. 12 Chem. 01 Chem. 10 0.3Balance 434 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7Sol. 16 Sol. 11 Surf. 13 Chem. 01 Chem. 07 0.3 Balance 435 10.0% 1.0%60% 10% 0.1% 10 ppt 10 ppt Example HA Amine 7 Sol. 16 Sol. 11 Surf. 14Chem. 03 Chem. 11 0.5 Balance 436 10.0% 1.0% 60% 10% 0.1% 10 ppt 10 pptExample HA TMAH Sol. 01 Surf. 05 Chem. 01 0.5 Balance 437 10.0% 1.0% 60%0.1% 10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 0.5 Balance 43810.0% 1.0% 60% 0.1% 500 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 010.6 Balance 439 10.0% 1.0% 60% 0.1% 5,000 ppt Example HA TMAH Sol. 01Surf. 05 Chem. 01 0.6 Balance 440 10.0% 1.0% 60% 0.1% 100 ppt Example HATMAH Sol. 01 Surf. 05 Chem. 01 0.8 Balance 441 10.0% 1.0% 60% 0.1% 5,000ppb Evaluation Formulation Residue pH Basic Co W Defect removal TemporalTemporal Table Adjusting HA/ compound/ ER ER suppression propertystability stability 1-25 agent pH surfactant surfactant (A/min) (A/min)property (0 h) (6 h) (12 h) Example Inorganic 11 100 10 2 1 B A B B 423acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 424acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 425acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 426acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 427acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 428acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 429acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 430acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 431acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 432acid/inorganic base Example Inorganic 11 100 10 4 2 B A B B 433acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 434acid/inorganic base Example Inorganic 11 100 10 2 1 B A B B 435acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 436acid/inorganic base Example Inorganic 11 100 10 3 2 B A B B 437acid/inorganic base Example Inorganic 11 100 10 3 2 A A B B 438acid/inorganic base Example Inorganic 11 100 10 4 2 A A B B 439acid/inorganic base Example Inorganic 11 100 10 4 2 A A B B 440acid/inorganic base Example Inorganic 11 100 10 5 3 B A B B 441acid/inorganic base

TABLE 26 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-26 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (ppb) Water Example HA TMAH Sol. 01 Surf. 05Chem. 02 0.8 Balance 442 10.0% 1.0% 60% 0.1% 10 ppt Example HA TMAH Sol.01 Surf. 05 Chem. 02 0.5 Balance 443 10.0% 1.0% 60% 0.1% 500 ppt ExampleHA TMAH Sol. 01 Surf. 05 Chem. 02 0.5 Balance 444 10.0% 1.0% 60% 0.1%5,000 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 02 0.5 Balance 44510.0% 1.0% 60% 0.1% 100 ppb Example HA TMAH Sol. 01 Surf. 05 Chem. 020.6 Balance 446 10.0% 1.0% 60% 0.1% 5,000 ppb Example HA TMAH Sol. 01Surf. 05 Chem. 01 Chem. 02 0.3 Balance 447 10.0% 1.0% 60% 0.1% 100 ppt100 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.3 Balance448 10.0% 1.0% 60% 0.1% 500 ppt 500 ppt Example HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 0.3 Balance 449 10.0% 1.0% 60% 0.1% 5000 ppt 5,000 pptExample HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.3 Balance 450 10.0%1.0% 60% 0.1% 100 ppb 100 ppb Example HA TMAH Sol. 01 Surf. 05 Chem. 01Chem. 02 0.5 Balance 451 10.0% 1.0% 60% 0.1% 5000 ppb 5,000 ppb ExampleHA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.8 0.3 Balance 452 10.0%1.0% 60% 0.1% 10 ppt 10 ppt ppt Example HA TMAH Sol. 01 Surf. 05 Chem.01 Chem. 02 8 0.5 Balance 453 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt pptExample HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 70 0.5 Balance 45410.0% 1.0% 60% 0.1% 10 ppt 10 ppt ppt Example HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 500 0.5 Balance 455 10.0% 1.0% 60% 0.1% 10 ppt 10 pptppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 5,000 0.5 Balance456 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt ppt Example HA TMAH Sol. 01 Surf.05 Chem. 01 Chem. 02 100 0.5 Balance 457 10.0% 1.0% 60% 0.1% 10 ppt 10ppt ppb Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1 0.5 Balance458 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt ppm Example HA TMAH Sol. 01 Surf.05 Chem. 01 Chem. 02 0.005% 0.5 Balance 459 10.0% 1.0% 60% 0.1% 10 ppt10 ppt Example HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.03%  0.3Balance 460 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Evaluation FormulationResidue pH Basic Co W Defect removal Temporal Temporal Table AdjustingHA/ compound/ ER ER suppression property stability stability 1-26 agentpH surfactant surfactant (A/min) (A/min) property (0 h) (6 h) (12 h)Example Inorganic 11 100 10 5 3 B A B B 442 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 443 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 444 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 445 acid/inorganic base ExampleInorganic 11 100 10 4 2 B A B B 446 acid/inorganic base ExampleInorganic 11 100 10 2 1 A A B B 447 acid/inorganic base ExampleInorganic 11 100 10 2 1 A A B B 448 acid/inorganic base ExampleInorganic 11 100 10 2 1 A A B B 449 acid/inorganic base ExampleInorganic 11 100 10 2 1 A A B B 450 acid/inorganic base ExampleInorganic 11 100 10 3 2 B A B B 451 acid/inorganic base ExampleInorganic 11 100 10 2 1 B A B B 452 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 453 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 454 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 455 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 456 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 457 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 458 acid/inorganic base ExampleInorganic 11 100 10 3 2 A A B B 459 acid/inorganic base ExampleInorganic 11 100 10 2 1 A A B B 460 acid/inorganic base

TABLE 27 Formulation Metal- Alcohol- Alcohol- Tertiary Alkyl containingTable Hydroxylamine Basic based based amine halide Acetic Otherparticles 1-27 compound compound solvent 1 solvent 2 Surfactant compoundcompound acid additives (PPb) Water Example 461 HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 0.12% 0.3 Balance 10.0% 1.0% 60% 0.1% 10 ppt 10 pptExample 462 HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.001 Balance10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example 463 HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 12 Balance 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Example464 HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 O.A.1 0.5 Balance 10.0%1.0% 60% 0.1% 10 ppt 10 ppt 0.5% Example 465 HA TMAH Sol. 01 Surf. 05Chem. 01 Chem. 02 Red. 1 0.6 Balance 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt0.5% Example 466 HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 Red. 2 0.3Balance 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt 0.5% Example 467 HA TMAH Sol.01 Surf. 05 Chem. 01 Chem. 02 Red. 3 0.5 Balance 10.0% 1.0% 60% 0.1% 10ppt 10 ppt 0.5% Example 468 HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02Red. 4 0.5 Balance 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt 0.5% Example 469 HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 0.06% 0.3 Balance 10.0% 1.0% 60%0.1% 10 ppt 10 ppt Comparative HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem.02 5 Balance Example 1 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt Comparative HATMAH Sol. 01 Surf. 05 Chem. 01 Chem. 02 1.5 Balance Example 2 10.0% 1.0%60% 0.1% 10 ppt 10 ppt Comparative HA TMAH Sol. 01 5.7 Balance Example 310.0% 1.0% 60% Comparative HA TMAH Sol. 01 Surf. 05 Chem. 01 Chem. 022.9 Balance Example 4 10.0% 1.0% 60% 0.1% 10 ppt 10 ppt EvaluationFormulation Residue pH Basic Co W Defect removal Temporal Temporal TableAdjusting HA/ compound/ ER ER suppression property stability stability1-27 agent pH surfactant surfactant (A/min) (A/min) property (0 h) (6 h)(12 h) Example 461 Inorganic 11 100 10 2 1 C A B B acid/inorganic baseExample 462 Inorganic 11 100 10 3 2 D A B B acid/inorganic base Example463 Inorganic 11 100 10 4 2 D A B B acid/inorganic base Example 464Inorganic 11 100 10 3 2 A A A A acid/inorganic base Example 465Inorganic 11 100 10 4 2 A A A A acid/inorganic base Example 466Inorganic 11 100 10 2 1 A A A A acid/inorganic base Example 467Inorganic 11 100 10 3 2 A A A A acid/inorganic base Example 468Inorganic 11 100 10 3 2 A A A A acid/inorganic base Example 469Inorganic 11 100 10 2 1 A A B B acid/inorganic base ComparativeInorganic 11 100 10 25 25 E C E E Example 1 acid/inorganic baseComparative Inorganic 11 100 10 6 9 E E A A Example 2 acid/inorganicbase Comparative Inorganic 11 12 45 E C A A Example 3 acid/inorganicbase Comparative Inorganic 7 100 10 21 8 E E A A Example 4acid/inorganic base

<Review of Results>

From the results shown in the tables, it was confirmed that the problemof the present invention could be solved by using the treatment liquidof the embodiment of the present invention.

It has been confirmed that in a case where the content of thealcohol-based solvent is 50% by mass or more with respect to the totalmass of the treatment liquid, the residue removal property, the defectsuppression property, the anticorrosion property, and the temporalstability tend to be more excellent, and in a case where the content ofthe alcohol-based solvent is 80% by mass or less, the defect suppressionproperty and the residue removal property tend to be more excellent (theresults of Examples 1 to 4, and the like).

It has been confirmed that in a case where the content of thehydroxylamine compound is 1% by mass or more (more preferably 6% by massor more) with respect to the total mass of the treatment liquid, thedefect suppression property and the residue removal property of thetreatment liquid tend to be more excellent.

It has been confirmed that in a case where the content of thehydroxylamine compound is 20% by mass or less (more preferably 15% bymass or less, and still more preferably 12% by mass or less) withrespect to the total mass of the treatment liquid, the residue removalproperty and the anticorrosion property of the treatment liquid tend tobe more excellent.

(The Results of Examples 2, and 5 to 13, and The Like)

It has been confirmed that in a case where the pH is 9 or more (morepreferably 10 or more, and still more preferably more than 10), theanticorrosion property against Co, the defect suppression property, andthe residue removal property of the treatment liquid tend to be moreexcellent.

It has been confirmed that in a case where the pH is 12 or less (morepreferably less than 12), the anticorrosion property against W and thedefect suppression property of the treatment liquid tend to be moreexcellent.

(The Results of Examples 2 and 14 to 18, and The Like)

It has been confirmed that in a case where a mass ratio of the contentof the hydroxylamine compound to the content of the surfactant in thetreatment liquid is 1 or more (more preferably 10 or more, and stillmore preferably 80 or more), the residue removal property, the defectsuppression property, the anticorrosion property, and the temporalstability of the treatment liquid tend to be more excellent, and in acase where the mass ratio is 1,000 or less (more preferably 150 or less,and still more preferably 250 or less), the residue removal property,the defect suppression property, and the temporal stability of thetreatment liquid tend to be more excellent.

(The Results of Examples 2, 5 to 13, and 191 to 196, and The Like)

It has been confirmed that in a case where a mass ratio of the contentof the organic basic compound to the content of the surfactant in thetreatment liquid is 1 or more (more preferably more than 1 and less than118), the anticorrosion property, the defect suppression property, theresidue removal property, and the temporal stability of the treatmentliquid tend to be more excellent.

(The Results of Examples 2, 191 to 194, and 196, and The Like)

It has been confirmed that in a case where the surfactant has a nitrogenatom (preferably in a case where the surfactant is a nonionic orcationic one), the defect suppression property and the residue removalproperty tend to be more excellent.

(The Results of Examples 2, and 173 to 190, and The Like)

It was confirmed that in a case where the content of the surfactant is 1ppm by mass or more (more preferably 85 ppm by mass or more, and stillmore preferably 0.01% by mass or more) and 2% by mass or less (morepreferably 1% by mass or less, and still more preferably 0.1% by mass orless) with respect to the total mass of the treatment liquid, the defectsuppression property, the residue removal property, and the temporalstability of the treatment liquid tend to be more excellent.

(The Results of Examples 2, 191 to 194, and 196, and The Like)

It was confirmed that in a case where the content of themetal-containing particles is 10 ppt by mass to 10 ppb by mass withrespect to the total mass of the treatment liquid, the defectsuppression property of the treatment liquid tends to be more excellent.

(The Results of Examples 2, 462, and 463, and The Like)

It was confirmed that in a case where the treatment liquid contains atertiary amine compound in an amount of 50 ppt by mass to 100 ppb bymass with respect to the total mass of the treatment liquid, the defectsuppression property tends to be more excellent.

(The Results of Examples 2, and 437 to 441, and The Like)

It was confirmed that in a case where the treatment liquid contains analkyl halide compound in an amount of 50 ppt by mass to 100 ppb by masswith respect to the total mass of the treatment liquid, the defectsuppression property tends to be more excellent.

(The Results of Examples 2, and 442 to 446, and The Like)

It was confirmed that in a case where the treatment liquid contains areducing agent, the defect suppression property and the temporalstability tend to be more excellent.

(The Results of Examples 2, and 465 to 468, and The Like)

It was confirmed that in a case where the treatment liquid containsacetic acid in an amount of 1 ppt by mass to 0.1% by mass with respectto the total mass of the treatment liquid, the defect suppressionproperty tends to be more excellent.

(The Results of Examples 2, 452 to 461, and 469, and The Like)

It was confirmed that in a case where the treatment liquid containsanother organic acid, the defect suppression property and the temporalstability tend to be more excellent.

(The Results of Examples 2 and 464, and The Like)

It was confirmed that in a case where the addition amount of theinorganic base used as a pH adjusting agent for increasing the pH of thetreatment liquid is 0.1% by mass or less with respect to the total massof the treatment liquid, a tendency of the same results as those in acase where the pH is adjusted by adjusting the addition amount of theorganic basic compound is exhibited.

(The Results of Examples 20 and 55, and The Like)

EXPLANATION OF REFERENCES

1: substrate

2: metal layer

3: etching stop layer

4: interlayer insulating layer

5: metal hard mask

6: hole

10: laminate

11: inner wall

11 a: cross-sectional wall

11 b: bottom wall

12: dry etching residue

What is claimed is:
 1. A treatment liquid for a semiconductor device,comprising: one or more hydroxylamine compounds selected from the groupconsisting of hydroxylamine and a hydroxylamine salt; an organic basiccompound; an alcohol-based solvent; and a surfactant, wherein thecontent of the alcohol-based solvent is 40% to 85% by mass with respectto the total mass of the treatment liquid, the pH is 8 or higher, andthe mass ratio of the content of the hydroxylamine compound to thecontent of the surfactant is 1 to 1,000.
 2. The treatment liquidaccording to claim 1, wherein the content of the hydroxylamine compoundis 1% to 20% by mass with respect to the total mass of the treatmentliquid.
 3. The treatment liquid according to claim 1, wherein theorganic basic compound includes one or more selected from the groupconsisting of tetramethylammonium hydroxide, tetrabutylammoniumhydroxide, benzyltrimethylammonium hydroxide, tetrahydrofurfurylamine,N-(2-aminoethyl)piperazine, 1,8-diazabicyclo[5.4.0]-7-undecene, and1,4-diazabicyclo[2.2.2]octane.
 4. The treatment liquid according toclaim 1, wherein the organic basic compound contains a tertiary aminecompound, the tertiary amine compound contains a tertiary amino groupother than a tertiary amino group contained in a nitrogen-containingnon-aromatic ring, and the content of the tertiary amine compound is 1ppt by mass to 5 ppm by mass with respect to the total mass of thetreatment liquid.
 5. The treatment liquid according to claim 1, whereinthe mass ratio of the content of the organic basic compound to thecontent of the surfactant is 1 to
 150. 6. The treatment liquid accordingto claim 1, wherein the surfactant is a cationic surfactant.
 7. Thetreatment liquid according to claim 6, wherein the cationic surfactantcontains a quaternary nitrogen atom.
 8. The treatment liquid accordingto claim 1, wherein the surfactant contains one or more selected fromthe group consisting of cetyltrimethylammonium bromide, cetylpyridiniumchloride, benzethonium chloride, chlorhexidine dihydrochloride,distearyldimethylammonium chloride, benzalkonium chloride, dequaliniumchloride, dodecyltrimethylammonium chloride, octadecylaminehydrochloride, and dodecylpyridinium chloride.
 9. The treatment liquidaccording to claim 1, wherein the content of the surfactant is 1 ppm bymass to 0.5% by mass with respect to the total mass of the treatmentliquid.
 10. The treatment liquid according to claim 1, wherein thealcohol-based solvent contains an alkoxy group.
 11. The treatment liquidaccording to claim 1, wherein the alcohol-based solvent contains one ormore selected from the group consisting of 3-methoxy-3-methyl 1-butanol,furfuryl alcohol, glycerin, 2-methyl-2,4-pentanediol, ethylene glycol,1,2-propanediol, ethylene glycol monoethyl ether, ethylene glycolmonobutyl ether, diethylene glycol monomethyl ether, diethylene glycolmonoethyl ether, and dipropylene glycol monomethyl ether.
 12. Thetreatment liquid according to claim 1, further comprising an alkylhalide compound, wherein the content of the alkyl halide compound is 1ppt by mass to 5 ppm by mass with respect to the total mass of thetreatment liquid.
 13. The treatment liquid according to claim 1, furthercomprising a reducing agent.
 14. The treatment liquid according to claim13, wherein the reducing agent is one or more reducing agents selectedfrom the group consisting of catechol and a derivative thereof, and amercaptan compound.
 15. The treatment liquid according to claim 1,further comprising acetic acid, wherein the content of the acetic acidis 1 ppt by mass to 0.1% by mass with respect to the total mass of thetreatment liquid.
 16. The treatment liquid according to claim 1, furthercomprising another organic acid other than acetic acid.
 17. Thetreatment liquid according to claim 1, further comprisingmetal-containing particles, wherein the metal-containing particlescontain one or more metal components selected from the group consistingof Na, Ca, Fe, and Cr, the particle diameter of the metal-containingparticles is 0.02 to 0.05 μm, and the content of the metal-containingparticles is 10 ppt by mass to 10 ppb by mass with respect to the totalmass of the treatment liquid.
 18. The treatment liquid according toclaim 1, used as a cleaning liquid for removing etching residues, asolution for removing a resist film used for pattern formation, or acleaning liquid for removing residues from a substrate after chemicalmechanical polishing.
 19. The treatment liquid according to claim 1,used for a treatment of a substrate having a metal layer containing oneor more selected from the group consisting of W and Co.
 20. A treatmentliquid for a semiconductor device, comprising: one or more hydroxylaminecompounds selected from the group consisting of hydroxylamine and ahydroxylamine salt; an organic basic compound; an alcohol-based solvent;and a surfactant, wherein the content of the alcohol-based solvent is40% to 85% by mass with respect to the total mass of the treatmentliquid, the pH is 8 or higher, the organic basic compound contains atertiary amine compound, the tertiary amine compound contains a tertiaryamino group other than a tertiary amino group contained in anitrogen-containing non-aromatic ring, and the content of the tertiaryamine compound is 1 ppt by mass to 5 ppm by mass with respect to thetotal mass of the treatment liquid.
 21. The treatment liquid accordingto claim 20, further comprising an alkyl halide compound, wherein thecontent of the alkyl halide compound is 1 ppt by mass to 5 ppm by masswith respect to the total mass of the treatment liquid.
 22. Thetreatment liquid according to claim 20, wherein the alkyl halidecompound consists of a hydrocarbon group and a halogen atom.